Self indicating antimicrobial chemistry

ABSTRACT

Self-indicating chemistries are provided for visual detection by a user of efficacious levels of peroxycarboxylic acid concentrations in a solution produced in situ. The self-indicating chemistries include a combination of dyes providing a visual color indication, such as a tri-color indicator system, such as a yellow, green, and red color system indicating in situ threshold levels of peroxycarboxylic acid concentrations in a solution employing the self-indicating chemistry. Systems, kits and compositions for a quantitative assessment of an in situ perhydrolysis reaction to generate peroxycarboxylic acids are provided. Methods of use are further provided.

RELATED APPLICATIONS

This application is a Continuation Application of U.S. application Ser.No. 16/353,355, filed Mar. 14, 2019, which is a Divisional Applicationof U.S. application Ser. No. 15/260,760, filed on Sep. 9, 2016, now U.S.Pat. No. 10,285,401, issued May 14, 2019, which claims priority to U.S.Provisional Application Ser. No. 62/216,435 filed on Sep. 10, 2015entitled “2-Part Self Indicating Antimicrobial Chemistry,” the entiredisclosures of which are incorporated herein by reference.

FIELD OF THE INVENTION

The invention relates to a self-indicating chemistry suitable fordetecting efficacious levels of peroxycarboxylic acid concentrations,namely for surface disinfection, in a solution in situ. In particular, acombination of dyes, namely a combination of at least two or three dyesto provide a tri-color indicator system. In an aspect, the tri-colorindicators are suitable for providing a series of yellow, green, and redcolors to indicate threshold levels of peroxycarboxylic acidconcentrations in a solution. The self-indicating chemistry compositionsprovide a proof of generation or proof of delivery of theperoxycarboxylic acid compositions employing the self-indicatingchemistry compositions. Beneficially, the self-indicating chemistrycompositions are non-catalytic and non-fluorescent. Methods of use areprovided.

BACKGROUND OF THE INVENTION

Among various biocides known, peroxycarboxylic acids are increasinglyused as antimicrobials and bleaching agents in many applications, owingto their high efficacy against a broad spectrum of microorganisms, colorsafe property, low residues and nontoxic nature of their decompositionproducts. Peracetic acid is the most commonly used peroxycarboxylic acidand has been shown to be a good biocide, but only at relatively highconcentrations (generally greater than 80 part per million). Similarly,peroxyfatty acids have also been shown to be biocidal, but only at highconcentrations (greater than 200 ppm). In contrast, peroxyformic acidhas an advantageous degree and range of microcidal properties comparedto other peroxycarboxylic acids, such as peracetic and perproprionicacids, as disclosed by V. Merka et al in J. Hyg. Epidem. Microbiol.Immunol., 1965 (IX) 220, as well as in European Patent Application No.863,098,96, which are incorporated herein by reference in theirentirety.

Most often, peroxycarboxylic acids are generated in a chemical plantthrough an acid catalyzed equilibrium reaction, and then shipped tocustomers for on-site use. Due to the limited storage stability ofperoxycarboxylic acids, the peroxycarboxylic acids must be packed inspecial containers and shipped under strict Department of Transportation(DOT) guidelines. Further, excess amounts of reagents (e.g., acids,oxidizing agents, and stabilizers) are present in these compositionsduring shipping to prevent decomposition. For certain peroxycarboxylicacids, such as peroxyformic acid, however, the inherent instability ofthe substance relative to the higher alkyl peracids, and the explosivenature of the substance at the concentrate make it an even moresignificant challenge to be manufactured, stored and transported beforedilution prior to use, in the similar way like higher alkyl peracids.Accordingly, peroxycarboxylic acids have alternatively been generated insitu through a perhydrolysis reaction of the higher alkyl carboxylicacid esters of polyhydric alcohol under strong alkaline conditions (e.g.pH greater than 12) and thereafter acidified to become an efficientbiocide, as disclosed in the Patent Application No. WO2012/090124 andU.S. Pat. No. 7,919,122, each of which are incorporated herein byreference in their entirety.

Such in situ generation of peroxycarboxylic acid biocides are thereaftersuitable for use when a sufficient concentration biocide is achieved.However, certain assays for peroxycarboxylic acid compositions aredestructive to the biocide concentration and therefore undesirable. Forexample, iodide is a destructive assay, as disclosed for example in U.S.Pat. No. 4,900,682. Moreover, other fluorescent tracers may bedestructive to peracid compositions. Fluorometric spectroscopy concernsthe detection of fluorescent light emitted by a sample and involvesusing a beam of light, usually ultraviolet (UV) light, that excites theelectrons in molecules of certain compounds in the sample and causesthem to emit light of a lower energy (i.e., to “fluoresce”). There areseveral types of fluorometers for measuring emitted fluorescence.Fluorometers generally have of a source of excitation radiant energy, anexcitation wavelength selector, a sample cell to contain the samplematerial, an emission wavelength selector, a detector with signalprocessor and a readout device. Filter fluorometers use optical filtersto isolate the incident light and fluorescent light. Spectrofluorometersuse diffraction grating monochromators to isolate the incident light andfluorescent light. One method of monitoring the concentration of achemical product (e.g., a cleaning agent) within a water sample relieson monitoring the fluorescence of the product that occurs when thesample (and the product within the sample) is exposed to a predeterminedwavelength of light. Accordingly, the use of fluorescent actives oftenrequires use of optical measuring devices. However it may be moredesirable to have a built-in quantitative measurement system as opposedto requiring a device, such as controller modules or other handhelddevices.

Accordingly, it is an objective of the invention to developself-indicating systems for use with on-site generation ofperoxycarboxylic acids to provide a visual indicator of peroxycarboxylicconcentration without destroying the peroxycarboxylic acid, includingfor example peroxyformic acids. In a further aspect, the invention issuitable for providing a visual indicator that further provides astabilizing effect on the peroxycarboxylic acid as opposed to adestructive effect.

A further object of the invention is to provide a method of indicatingcompletion of a peroxycarboxylic acid generated by perhydrolysis in situthrough a visual indication to a user, including a non-fluorescentmarker or indicator, and a non-catalytic or destructive indicator.

It further is an object of this invention to provide for a quick visualscreening procedure to screen and test toxicants and biocides useful incontrol of microorganism growth and provide for control or eliminationof microorganism growth.

Other objects, advantages and features of the present invention willbecome apparent from the following specification taken in conjunctionwith the accompanying drawings.

BRIEF SUMMARY OF THE INVENTION

The present invention relates generally to peroxycarboxylic acidcompositions, such as peroxyformic acid compositions, employing aself-indicating chemistry suitable for detecting efficacious levels ofperoxycarboxylic acid concentrations in a solution in situ.Beneficially, the self-indicating chemistry compositions arenon-destructive to the peroxycarboxylic acid compositions. In certainembodiments, the self-indicating chemistry compositions provide astabilizing effect on the peroxycarboxylic acid concentrations. Methodsof providing a visual indication of completion of a perhydrolysisreaction to generate a peroxycarboxylic acid composition employing athree dye system are provided. Methods of using the peroxycarboxylicacid compositions having a self-indicating chemistry for treating aretarget are further provided. An advantage of the invention is the visualassessment provided by a tri-color indicator system providing a user aclear basis to confirm a sufficient level of the peroxycarboxylic acidbiocide has been produced in situ, and confirm when a peroxycarboxylicacid biocide concentration has decreased below a thresholdconcentration(s).

In an embodiment a self-indicating peroxycarboxylic acid chemistrycomposition comprises: a peroxycarboxylic acid; a background dye; and alatent peracid selective dye(s) which upon oxidation by theperoxycarboxylic acid provides a visual indication the presence of aminimum concentration of peroxycarboxylic acid for efficacy as anantimicrobial.

In an embodiment a method of generating a self-indicatingperoxycarboxylic acid composition for surface disinfection comprises:contacting a first reagent with a second reagent, wherein the firstreagent comprises at least one ester of a polyhydric alcohol and aC1-C18 carboxylic acid, and wherein the second reagent compriseshydrogen peroxide or a substance that generates hydrogen peroxide;generating a peroxycarboxylic acid in situ by perhydrolysis; andindicating a presence of a minimum concentration of the peroxycarboxylicacid through a non-fluorescent visual indicator comprising at least twodyes in the peroxycarboxylic acid, wherein the first reagent and saidsecond reagent are kept separate prior to use.

In an embodiment a method of indicating the presence of aperoxycarboxylic acid concentration for surface disinfection comprises:generating a peroxycarboxylic acid in situ by perhydrolysis; contactinga latent dye of a visual indicator composition with a peroxycarboxylicacid to oxidize the latent dye; and indicating a presence of a desiredconcentration of the peroxycarboxylic acid for surface disinfectionthrough the visual indicator composition comprising at least two dyes,wherein the combination of dyes have different half-lives to providesustained visual indication of peroxycarboxylic acid concentration forat least 12 hours.

In an embodiment a kit comprises: a first reagent comprising at leastone ester of a polyhydric alcohol and a C1-C18 carboxylic acid; a secondreagent comprising hydrogen peroxide or a substance that generateshydrogen peroxide; and a non-fluorescent visual indicator comprising atleast two dyes for providing a visual color indication correlated to aconcentration of peroxycarboxylic acid, wherein the visual indicator canbe a third reagent or combined with the first reagent; wherein combiningthe first reagent and the second reagent generates a peroxycarboxylicacid in situ by perhydrolysis reaction and the presence of thenon-fluorescent visual indicator provides a color indication of thepresence of a minimum concentration of the peroxycarboxylic acid forsurface disinfection.

While multiple embodiments are disclosed, still other embodiments of thepresent invention will become apparent to those skilled in the art fromthe following detailed description, which shows and describesillustrative embodiments of the invention. Accordingly, the drawings anddetailed description are to be regarded as illustrative in nature andnot restrictive.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a UV-VIS scan at 30 second intervals and respectiveabsorptions depicting a performic acid visual indicator system accordingto embodiments of the invention.

FIG. 2 shows a graph of measured peroxyformic acid concentration overtime (20 minutes) depicting a stabilizing effect of the visual indicatorsystem according to embodiments of the invention on performic acid.

FIG. 3 shows a graph of measured half-lives of preferred dyes for theself-indicating chemistry compositions as referred to as a degenerationgraph according to embodiments of the invention on performic acid.

The patent or application file contains at least one drawing executed incolor. Copies of this patent or patent application publication withcolor drawing(s) will be provided by the Office upon request and paymentof the necessary fee. Various embodiments of the present invention willbe described in detail with reference to the drawings, wherein likereference numerals represent like parts throughout the several views.Reference to various embodiments does not limit the scope of theinvention. Figures represented herein are not limitations to the variousembodiments according to the invention and are presented for exemplaryillustration of the invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The embodiments of this invention are not limited to particularperoxycarboxylic acid compositions or self-indicating chemistries foruse with peroxycarboxylic acid compositions, which can vary and areunderstood by skilled artisans. It is further to be understood that allterminology used herein is for the purpose of describing particularembodiments only, and is not intended to be limiting in any manner orscope. For example, as used in this specification and the appendedclaims, the singular forms “a,” “an” and “the” can include pluralreferents unless the content clearly indicates otherwise. Further, allunits, prefixes, and symbols may be denoted in its SI accepted form.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as is commonly understood by one of ordinary skillin the art to which this invention belongs. All patents, applications,published applications and other publications referred to herein areincorporated by reference in their entireties. If a definition set forthin this section is contrary to or otherwise inconsistent with adefinition set forth in the patents, applications, publishedapplications and other publications that are herein incorporated byreference, the definition set forth in this section prevails over thedefinition that is incorporated herein by reference.

So that the present invention may be more readily understood, certainterms are first defined. Unless defined otherwise, all technical andscientific terms used herein have the same meaning as commonlyunderstood by one of ordinary skill in the art to which embodiments ofthe invention pertain. Many methods and materials similar, modified, orequivalent to those described herein can be used in the practice of theembodiments of the present invention without undue experimentation, thepreferred materials and methods are described herein. In describing andclaiming the embodiments of the present invention, the followingterminology will be used in accordance with the definitions set outbelow.

Numeric ranges recited within the specification are inclusive of thenumbers within the defined range. Throughout this disclosure, variousaspects of this invention are presented in a range format. It should beunderstood that the description in range format is merely forconvenience and brevity and should not be construed as an inflexiblelimitation on the scope of the invention. Accordingly, the descriptionof a range should be considered to have specifically disclosed all thepossible sub-ranges as well as individual numerical values within thatrange (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

The term “about,” as used herein, refers to variation in the numericalquantity that can occur, for example, through typical measuring andliquid handling procedures used for making concentrates or use solutionsin the real world; through inadvertent error in these procedures;through differences in the manufacture, source, or purity of theingredients used to make the compositions or carry out the methods; andthe like. The term “about” also encompasses amounts that differ due todifferent equilibrium conditions for a composition resulting from aparticular initial mixture. Whether or not modified by the term “about”,the claims include equivalents to the quantities.

The term “actives” or “percent actives” or “percent by weight actives”or “actives concentration” are used interchangeably herein and refers tothe concentration of those ingredients involved in cleaning expressed asa percentage minus inert ingredients such as water or salts.

As used herein, the term “alkyl” or “alkyl groups” refers to saturatedhydrocarbons having one or more carbon atoms, including straight-chainalkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, etc.), cyclic alkyl groups (or “cycloalkyl” or“alicyclic” or “carbocyclic” groups) (e.g., cyclopropyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, etc.), branched-chain alkyl groups(e.g., isopropyl, tert-butyl, sec-butyl, isobutyl, etc.), andalkyl-substituted alkyl groups (e.g., alkyl-substituted cycloalkylgroups and cycloalkyl-substituted alkyl groups).

Unless otherwise specified, the term “alkyl” includes both“unsubstituted alkyls” and “substituted alkyls.” As used herein, theterm “substituted alkyls” refers to alkyl groups having substituentsreplacing one or more hydrogens on one or more carbons of thehydrocarbon backbone. Such substituents may include, for example,alkenyl, alkynyl, halogeno, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy,alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate,alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl,phosphate, phosphonato, phosphinato, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino),acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyland ureido), imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate,sulfates, alkylsulfinyl, sulfonates, sulfamoyl, sulfonamido, nitro,trifluoromethyl, cyano, azido, heterocyclic, alkylaryl, or aromatic(including heteroaromatic) groups. In some embodiments, substitutedalkyls can include a heterocyclic group. As used herein, the term“heterocyclic group” includes closed ring structures analogous tocarbocyclic groups in which one or more of the carbon atoms in the ringis an element other than carbon, for example, nitrogen, sulfur oroxygen. Heterocyclic groups may be saturated or unsaturated. Exemplaryheterocyclic groups include, but are not limited to, aziridine, ethyleneoxide (epoxides, oxiranes), thiirane (episulfides), dioxirane,azetidine, oxetane, thietane, dioxetane, dithietane, dithiete,azolidine, pyrrolidine, pyrroline, oxolane, dihydrofuran, and furan.

The term “alkenyl” includes an unsaturated aliphatic hydrocarbon chainhaving from 2 to 12 carbon atoms, such as, for example, ethenyl,1-propenyl, 2-propenyl, 1-butenyl, 2-methyl-1-propenyl, and the like.The alkyl or alkenyl can be terminally substituted with a heteroatom,such as, for example, a nitrogen, sulfur, or oxygen atom, forming anaminoalkyl, oxyalkyl, or thioalkyl, for example, aminomethyl, thioethyl,oxypropyl, and the like. Similarly, the above alkyl or alkenyl can beinterrupted in the chain by a heteroatom forming an alkylaminoalkyl,alkylthioalkyl, or alkoxyalkyl, for example, methylaminoethyl,ethylthiopropyl, methoxymethyl, and the like.

Further, as used herein the term “alicyclic” includes any cyclichydrocarbyl containing from 3 to 8 carbon atoms. Examples of suitablealicyclic groups include cyclopropanyl, cyclobutanyl, cyclopentanyl,etc. The term “heterocyclic” includes any closed ring structuresanalogous to carbocyclic groups in which one or more of the carbon atomsin the ring is an element other than carbon (heteroatom), for example, anitrogen, sulfur, or oxygen atom. Heterocyclic groups may be saturatedor unsaturated. Examples of suitable heterocyclic groups include forexample, aziridine, ethylene oxide (epoxides, oxiranes), thiirane(episulfides), dioxirane, azetidine, oxetane, thietane, dioxetane,dithietane, dithiete, azolidine, pyrrolidine, pyrroline, oxolane,dihydrofuran, and furan. Additional examples of suitable heterocyclicgroups include groups derived from tetrahydrofurans, furans, thiophenes,pyrrolidines, piperidines, pyridines, pyrrols, picoline, coumaline, etc.

In some embodiments, alkyl, alkenyl, alicyclic groups, and heterocyclicgroups can be unsubstituted or substituted by, for example, aryl,heteroaryl, C₁₋₄ alkyl, C₁₋₄ alkenyl, C₁₋₄ alkoxy, amino, carboxy, halo,nitro, cyano, —SO₃H, phosphono, or hydroxy. When alkyl, alkenyl,alicyclic group, or heterocyclic group is substituted, preferably thesubstitution is C₁₋₄ alkyl, halo, nitro, amido, hydroxy, carboxy,sulpho, or phosphono. In one embodiment, R includes alkyl substitutedwith hydroxy. The term “aryl” includes aromatic hydrocarbyl, includingfused aromatic rings, such as, for example, phenyl and naphthyl. Theterm “heteroaryl” includes heterocyclic aromatic derivatives having atleast one heteroatom such as, for example, nitrogen, oxygen, phosphorus,or sulfur, and includes, for example, furyl, pyrrolyl, thienyl,oxazolyl, pyridyl, imidazolyl, thiazolyl, isoxazolyl, pyrazolyl,isothiazolyl, etc. The term “heteroaryl” also includes fused rings inwhich at least one ring is aromatic, such as, for example, indolyl,purinyl, benzofuryl, etc.

In some embodiments, aryl and heteroaryl groups can be unsubstituted orsubstituted on the ring by, for example, aryl, heteroaryl, alkyl,alkenyl, alkoxy, amino, carboxy, halo, nitro, cyano, —SO₃H, phosphono,or hydroxy. When aryl, aralkyl, or heteroaryl is substituted, preferablythe substitution is C1-4 alkyl, halo, nitro, amido, hydroxy, carboxy,sulpho, or phosphono. In one embodiment, R includes aryl substitutedwith C₁₋₄ alkyl.

As used herein, the term “cleaning” refers to a method used tofacilitate or aid in soil removal, bleaching, microbial populationreduction, and any combination thereof. For the purpose of this patentapplication, successful microbial reduction is achieved when themicrobial populations are reduced by at least about 50%, or bysignificantly more than is achieved by a wash with water. Largerreductions in microbial population provide greater levels of protection.

As used herein, the term “disinfectant” refers to an agent that killsall vegetative cells including most recognized pathogenicmicroorganisms, using the procedure described in A.O.A.C. Use DilutionMethods, Official Methods of Analysis of the Association of OfficialAnalytical Chemists, paragraph 955.14 and applicable sections, 15thEdition, 1990 (EPA Guideline 91-2). As used herein, the term “high leveldisinfection” or “high level disinfectant” refers to a compound orcomposition that kills substantially all organisms, except high levelsof bacterial spores, and is effected with a chemical germicide clearedfor marketing as a sterilant by the Food and Drug Administration. Asused herein, the term “intermediate-level disinfection” or “intermediatelevel disinfectant” refers to a compound or composition that killsmycobacteria, most viruses, and bacteria with a chemical germicideregistered as a tuberculocide by the Environmental Protection Agency(EPA). As used herein, the term “low-level disinfection” or “low leveldisinfectant” refers to a compound or composition that kills someviruses and bacteria with a chemical germicide registered as a hospitaldisinfectant by the EPA.

As used herein, the term “free,” “no,” “substantially no” or“substantially free” refers to a composition, mixture, or ingredientthat does not contain a particular compound or to which a particularcompound or a particular compound-containing compound has not beenadded. In some embodiments, the reduction and/or elimination of hydrogenperoxide according to embodiments provide hydrogen peroxide-free orsubstantially-free compositions. Should the particular compound bepresent through contamination and/or use in a minimal amount of acomposition, mixture, or ingredients, the amount of the compound shallbe less than about 3 wt-%. More preferably, the amount of the compoundis less than 2 wt-%, less than 1 wt-%, and most preferably the amount ofthe compound is less than 0.5 wt-%.

As used herein, the term “microorganism” refers to any noncellular orunicellular (including colonial) organism. Microorganisms include allprokaryotes. Microorganisms include bacteria (including cyanobacteria),spores, lichens, fungi, protozoa, virinos, viroids, viruses, phages, andsome algae. As used herein, the term “microbe” is synonymous withmicroorganism.

As used herein, the terms “mixed” or “mixture” when used relating to“percarboxylic acid composition,” “percarboxylic acids,”“peroxycarboxylic acid composition” or “peroxycarboxylic acids” refer toa composition or mixture including more than one percarboxylic acid orperoxycarboxylic acid.

As used herein, the term “sanitizer” refers to an agent that reduces thenumber of bacterial contaminants to safe levels as judged by publichealth requirements. In an embodiment, sanitizers for use in thisinvention will provide at least a 3 log reduction and more preferably a5-log order reduction. These reductions can be evaluated using aprocedure set out in Germicidal and Detergent Sanitizing Action ofDisinfectants, Official Methods of Analysis of the Association ofOfficial Analytical Chemists, paragraph 960.09 and applicable sections,15th Edition, 1990 (EPA Guideline 91-2). According to this reference asanitizer should provide a 99.999% reduction (5-log order reduction)within 30 seconds at room temperature, 25±2° C., against several testorganisms.

Differentiation of antimicrobial “-cidal” or “-static” activity, thedefinitions which describe the degree of efficacy, and the officiallaboratory protocols for measuring this efficacy are considerations forunderstanding the relevance of antimicrobial agents and compositions.Antimicrobial compositions can affect two kinds of microbial celldamage. The first is a lethal, irreversible action resulting in completemicrobial cell destruction or incapacitation. The second type of celldamage is reversible, such that if the organism is rendered free of theagent, it can again multiply. The former is termed microbiocidal and thelater, microbistatic. A sanitizer and a disinfectant are, by definition,agents which provide antimicrobial or microbiocidal activity. Incontrast, a preservative is generally described as an inhibitor ormicrobistatic composition

The term “substantially similar cleaning performance” refers generallyto achievement by a substitute cleaning product or substitute cleaningsystem of generally the same degree (or at least not a significantlylesser degree) of cleanliness or with generally the same expenditure (orat least not a significantly lesser expenditure) of effort, or both.

As used herein, the term “sulfoperoxycarboxylic acid,” “sulfonatedperacid,” or “sulfonated peroxycarboxylic acid” refers to theperoxycarboxylic acid form of a sulfonated carboxylic acid. In someembodiments, the sulfonated peracids of the present invention aremid-chain sulfonated peracids. As used herein, the term “mid-chainsulfonated peracid” refers to a peracid compound that includes asulfonate group attached to a carbon that is at least one carbon (e.g.,the three position or further) from the carbon of the percarboxylic acidgroup in the carbon backbone of the percarboxylic acid chain, whereinthe at least one carbon is not in the terminal position. As used herein,the term “terminal position,” refers to the carbon on the carbonbackbone chain of a percarboxylic acid that is furthest from thepercarboxyl group.

As used herein, the term “waters” includes food process or transportwaters. Food process or transport waters include produce transportwaters (e.g., as found in flumes, pipe transports, cutters, slicers,blanchers, retort systems, washers, and the like), belt sprays for foodtransport lines, boot and hand-wash dip-pans, third-sink rinse waters,and the like. Waters also include domestic and recreational waters suchas pools, spas, recreational flumes and water slides, fountains, and thelike.

The term “weight percent,” “wt-%,” “percent by weight,” “% by weight,”and variations thereof, as used herein, refer to the concentration of asubstance as the weight of that substance divided by the total weight ofthe composition and multiplied by 100. It is understood that, as usedhere, “percent,” “%,” and the like are intended to be synonymous with“weight percent,” “wt-%,” etc.

The methods, systems, and compositions of the present invention maycomprise, consist essentially of, or consist of the components andingredients of the present invention as well as other ingredientsdescribed herein. As used herein, “consisting essentially of” means thatthe methods, systems, and compositions may include additional steps,components or ingredients, but only if the additional steps, componentsor ingredients do not materially alter the basic and novelcharacteristics of the claimed methods, systems, and compositions.

Compositions

The compositions and methods employing the compositions according to theinvention include a self-indicating chemistry composition suitable foruse with a peroxycarboxylic acid composition. In an aspect, theself-indicating chemistry composition comprises a combination of threedyes, and the peroxycarboxylic acid forming composition comprises atleast two reagents, wherein a first reagent comprises an ester of apolyhydric alcohol and a carboxylic acid, and wherein a second reagentcomprises hydrogen peroxide or a hydrogen peroxide source. In an aspect,the self-indicating chemistry composition is combined with the firstreagent. In a further aspect, the self-indicating chemistry and thefirst reagent are combined with the second reagent to generate a desiredperoxycarboxylic acid in the presence of the self-indicating chemistrycompositions to provide visual indicators to a user of theconcentrations of the peroxycarboxylic acid.

Self-Indicating Chemistry Compositions

In an aspect, the self-indicating chemistry compositions comprise acombination of at least two dyes. In a further aspect, theself-indicating chemistry compositions comprise a combination of threedyes. In a further aspect, the combination of dyes provides a visualindication system suitable for detecting the formation or generation ofa peroxycarboxylic acid formed in a perhydrolysis reaction. Preferably,the combination of dyes provides a visual indication system using threedistinct colors (e.g. blue, green, yellow). In an aspect, thecombination of dyes provides a non-fluorescent visual indicator for theperoxycarboxylic acid compositions. In a further aspect, the combinationof dyes are non-staining to a treated system.

Suitable dyes for use in the self-indicating chemistry compositioninclude oxidize able dyes, including those insensitive to hydrogenperoxide driving a perhydrolysis reaction to generate a peroxycarboxylicacid composition. In an aspect, the self-indicating chemistrycomposition include a combination of dyes having different half-lives inorder to provide sustained visual indicators, such as for up to 7 days,or from 1 to 7 days, or from 12 hours to 7 days. In an aspect, theself-indicating chemistry composition include a combination of HRPsubstrates and synthetic dyes. In an aspect, the HRP substrates providea long half-life and as the latent chromophore which does not result ina color (e.g. green) until oxidation the self-indicating chemistrycomposition is able to retain a visual indicator of the presence of theperoxycarboxylic acid concentration for up to 7 days, or from 1 to 7days, or from 12 hours to 7 days due to the half-life of the HRPsubstrate. Exemplary half-lives for the exemplary dyes employed in theself-indicating chemistry compositions are shown below in Examples.

Latent Peracid Selective Dyes and HRP Substrates

In an aspect, the self-indicating chemistry composition includes atleast one latent peracid selective dyes. In a further aspect, the latentperacid selective dye is a peroxide sensitive dye. In a further aspect,the latent peracid selective dye is a horse radish peroxidase enzyme(HRP) substrate. In a further aspect, the latent peracid selective dyeis a peroxide and horse radish peroxidase enzyme (HRP) substrate toprovide a yellow visual indicator. In an aspect, the yellow visualindicator is a latent dye which is selective for peroxycarboxylic acids.Suitable commercially-available latent peracid selective dyes (and HRPsubstrates) include PNPP (p-Nitrophenyl Phosphate, Disodium Salt), ABTS(2,2′-Azinobis [3-ethylbenzothiazoline-6-sulfonic acid]-diammonium salt)CAS 30931-67-0, OPD (o-phenylenediamine dihydrochloride), and TMB(3,3′,5,5′-tetramethylbenzidine) CAS 54827-17-7.

Additional latent peracid selective dyes suitable for use according tothe invention include latent chromophores which have been shown to besensitive to oxidation by hydrogen peroxide in the presence of HRP andwhich presumably will show peracid sensitivity, including the following:

Amplex Red (Resazurin) 7-hydroxy-10-oxidophenoxazin-10-ium-3-one;

Homovanillic acid (3-methoxy-4-hydroxyphenyl acetic acid);

AEC (3-amino-9-ethylcarbazole);

DAB (Diaminobenzidine); and

Compounds depicted in the following formulas:

In some aspects it is desirable to employ a combination of dyes havingdifferent light absorbance, yielding different colors and/or differentrates of color generation. In an aspect, it is desirable to have a firstHRP substrate yielding a color within a matter of seconds and a secondHRP substrate yielding a color within a matter of minutes. For example:PNPP produces a yellow water-soluble reaction product that absorbs lightat 405 nm; ABTS (2,2′-Azinobis [3-ethylbenzothiazoline-6-sulfonicacid]-diammonium salt) produces a green water-soluble reaction productthat has two major absorbance peaks at 410 nm and 650 nm and providesslow color development; OPD (o-phenylenediamine dihydrochloride)produces a yellow-orange water soluble reaction product with anabsorbance maximum of 492 nm; and TMB (3,3′,5,5′-tetramethylbenzidine)yields a soluble blue color and has an absorbance maxima or the reactionproduct are 370 nm and 652 nm, wherein the color then changes to yellowwith the addition of sulfuric or phosphoric acid with maximum absorbanceat 450 nm.

In an aspect, self-indicating chemistry composition includes at leastone HRP substrate selected from the group consisting of PNPP(p-Nitrophenyl Phosphate, Disodium Salt), ABTS (2,2′-Azinobis[3-ethylbenzothiazoline-6-sulfonic acid]-diammonium salt), OPD(o-phenylenediamine dihydrochloride), TMB(3,3′,5,5′-tetramethylbenzidine), and combinations thereof. In a furtheraspect, self-indicating chemistry composition includes at least two HRPsubstrates selected from the group consisting of PNPP (p-NitrophenylPhosphate, Disodium Salt), ABTS (2,2′-Azinobis[3-ethylbenzothiazoline-6-sulfonic acid]-diammonium salt), OPD(o-phenylenediamine dihydrochloride), TMB(3,3′,5,5′-tetramethylbenzidine), and combinations thereof.

In an aspect, the self-indicating chemistry compositions include twolatent peracid selective dyes having a ratio of from about 1:5 to 5:1,from about 1:3 to 3:1, or from about 1:2 to 2:1.

In an aspect, the self-indicating chemistry compositions include twolatent peracid selective dyes having a ratio of about 1:3 to 3:1, orpreferably 2:3 to 3:2, and more preferably about 2:3 (TMB:ABTS) whichbeneficially provides a near optimum generation of an intense yellowvisual indicator (via TMB) and is removed by bleaching of the ABTS toprovide the sustained oxidized dye according to the invention.

In an aspect, the self-indicating chemistry compositions include fromabout 0.0001 wt-%-5 wt-% of one or more latent peracid selective dyes,from about 0.0001 wt-%-0.001 wt-% of one or more latent peracidselective dyes, or preferably from about 0.0001 wt-%-0.1 wt-% of one ormore latent peracid selective dyes. In addition, without being limitedaccording to the invention, all ranges recited are inclusive of thenumbers defining the range and include each integer within the definedrange.

Background Dye

In an aspect, the self-indicating chemistry composition include at leastbackground dye to provide a green visual indicator. As referred toherein, background dyes are produced using aromatic hydrocarbons frompetroleum. Exemplary and non-limiting suitable commercially-availablebackground dyes include FD&C Blue No. 1 having the formulaC₃₇H₃₄N₂Na₂O₉S₃(ethyl-[4-[[4-[ethyl-[(3-sulfophenyl)methyl]amino]phenyl]-(2-sulfophenyl)methylidene]-1-cyclohexa-2,5-dienylidene]-[(3-sulfophenyl)methyl]azanium),Acid Blue 9, D&C Blue No. 4, Atracid Blue FG, Erioglaucine, Erioskyblue, Patent Blue AR, Xylene Blue VSG, and the like.

A background dye may be selected based upon desired characteristic ofits half-life to correlate a visual indicator with the concentrations ofa peroxycarboxylic acid composition in the self-indicating chemistrycomposition.

In an aspect, the background dye may be visible at time zero andthereafter fade in the self-indicating peracid chemistry composition. Inanother aspect, the background dye resists fading or bleaching.

In an aspect, the self-indicating chemistry compositions include abackground dye in addition to the latent peracid selective dyes, whereinthe ratio of the latent peracid selective dyes to the background dye isfrom about 20:1 to 1:1, from about 15:1 to 1:1, from about 15:1 to 5:1,from about 15:1 to 10:1, or about 10:1.

In an aspect, the self-indicating chemistry composition include fromabout 0.001 wt-%-1 wt-% of one or more synthetic dyes, from about 0.005wt-%-0.5 wt-% of one or more synthetic dyes, from about 0.01 wt-%-0.5wt-% of one or more synthetic dyes, preferably from about 0.01 wt-%-0.1wt-% of one or more synthetic dyes. In addition, without being limitedaccording to the invention, all ranges recited are inclusive of thenumbers defining the range and include each integer within the definedrange.

Peroxycarboxylic Acid Forming Compositions

The present invention relates to peroxycarboxylic acid formingcompositions suitable for use with self-indicating chemistrycompositions and uses thereof. In one aspect, the present invention isdirected to a peroxycarboxylic acid forming composition comprising: afirst reagent that comprises an ester of a polyhydric alcohol and acarboxylic acid, and a second reagent that comprises hydrogen peroxideor that comprises a substance that generates hydrogen peroxide when incontact with a liquid. In a further aspect, the first reagent furthercomprises the self-indicating chemistry composition. In a furtheraspect, the first reagent and second reagent are kept separately priorto use and combined when it is time to generate the peroxycarboxylicacid.

In an aspect, the first reagent is provided in amount from about 1% toabout 10%, preferably from about 2% to about 5%. In an aspect, thesecond reagent is provided in amount from about 90% to about 99%,preferably from about 95% to about 98%.

Table 1 shows exemplary ranges of the total weight-percentage of thecomponents for use in the combined amounts of the first and secondreagents according to the peroxycarboxylic acid forming compositions ofthe invention.

TABLE 1 First Exemplary Second Exemplary Third Exemplary EmbodimentEmbodiment Embodiment Ester of Polyhydric 0.1-50% 0.5-20% 1-10% Alcoholand Carboxylic Acid Hydrogen Peroxide 0.1-50% 0.5-20% 1-10%Self-Indicating 0.0001-5%  0.0001-0.1000%     0.0001-0.001%     Chemistry Composition Additional Functional 0.01-10 0.1-10.0001-0.2%     Ingredients (e.g. acidulant, stabilizers, buffers)

In a still further aspect, the first reagent and second reagent areconfigured to be contacted with each other to form a liquid thatcomprises a peroxycarboxylic acid and has a pH ranging from about 0 toabout 11, and pH of the formed liquid becomes about 8 or lower withinabout 1 minute after the contact between said first reagent and saidsecond reagent. In an alternative aspect, the second reagent comprises asubstance that generates hydrogen peroxide when in contact with aliquid, the first reagent and second reagent are comprised in a solidcomposition, and when it is time to generate the peroxycarboxylic acid,the solid composition is configured to be contacted with a liquid toform a liquid that comprises the peroxycarboxylic acid and has a pHranging from about 0 to about 11, and pH of the formed liquid becomesabout 8 or lower within about 1 minute after the contact between saidsolid composition and said liquid.

Esters of polyhydric alcohols and a C1-C18 carboxylic acid are includedin the first reagent. A polyhydric alcohol refers to an molecule withtwo or more hydroxyl (—OH) groups. An ester of a polyhydric alcohol anda carboxylic acid refers to an ester formed between a polyhydric alcoholand the carboxylic acid. A variety of carboxylic acids can be included.Carboxylic acids generally have the formula R(COOH)_(n), where, forexample, R is an alkyl, aryl alkyl, cycloalkyl, aromatic, orheterocyclic group, and n is one, two, or three.

In an embodiment the polyhydric alcohol may include a sugar alcohol. Inan embodiment where the peroxycarboxylic acid is peroxyformic, the firstreagent may comprise glycerol formates, pentaerythritol formats,mannitol formats, propylene glycol formates, sorbitol formates and sugarformates. In such an exemplary embodiment, any suitable sugar formatsmay be employed, e.g., sucrose formates, dextrin formates, maltodextrinformates, or starch formates.

The compositions can also include more than one or a mixture of estersof a polyhydric alcohol and a carboxylic acid. For example, in someembodiments, the compositions include two, three or four esters. Whenmore than one ester is present, the esters can be different. Forexample, in some embodiments, the compositions can include a first esterof a polyhydric alcohol and a C1 to C4 carboxylic acid, and a secondester of a polyhydric alcohol and a C5 to C11 carboxylic acid. Forfurther example, in some embodiments, the compositions can include afirst ester of a polyhydric alcohol and a C1 to C18 carboxylic acid in amono, di or tri-formation, and a second ester of a polyhydric alcoholand a C1 to C18 carboxylic acid in a mono, di or tri-formation. Oneskilled in the art will appreciate the various combinations of estersthat can be used for the compositions according to the invention.

The use of various forms of an ester (e.g. mono, di and/ortri-formations) to comprise a mixture of esters will impact the peracidyield of a particular composition according to the invention. Forexample, the various forms of the ester will have different kinetics ingenerating the peracids according to the methods of the invention. Forexample, in one aspect, a monooctanoate glycerol ester is faster ingenerating peracid than the di- or trioctanoate glycerol esters. Inaddition, the selection of the various forms of an ester will be furtherimpacted by the water solubility of the compositions and whether anyadditional ingredients are combined to affect solubility (e.g. solvents)that would favor the use of less soluble ester forms (e.g.tri-formations). Accordingly, one skilled in the art of reactionkinetics will ascertain the benefits of using various combinations ormixtures of esters according to the compositions and methods of theinvention.

Examples of suitable carboxylic acids include, but are not limited to,formic, acetic, propionic, butanoic, pentanoic, hexanoic, heptanoic,octanoic, nonanoic, decanoic, undecanoic, dodecanoic, as well as theirbranched isomers, lactic, maleic, ascorbic, citric, hydroxyacetic,neopentanoic, neoheptanoic, neodecanoic, oxalic, malonic, succinic,glutaric, adipic, pimelic subric acid, and mixtures thereof.

The peroxycarboxylic acid forming compositions can comprise any suitablelevel of an ester of a polyhydric alcohol and carboxylic acid (includingeither liquid or solid reagents). For example, the first reagent of theperoxycarboxylic acid forming composition can comprise any suitablelevel of an ester of a polyhydric alcohol and carboxylic acid. In someembodiments, the first reagent can comprise from about 10 ppm to about500,000 ppm of an ester of a polyhydric alcohol and carboxylic acid. Forexample, the first reagent can comprise from about 10-20 ppm, 20-30 ppm,30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm, 70-80 ppm, 80-90 ppm, 90-100ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm, 250-300 ppm, 300-350 ppm,350-400 ppm, 400-450 ppm, 450-500 ppm, 500-550 ppm, 550-600 ppm, 600-650ppm, 650-700 ppm, 700-750 ppm, 750-800 ppm, 800-850 ppm, 850-900 ppm,900-950 ppm, 950-1,000 ppm, 1,000-1,500 ppm, 1,500-2,000 ppm,2,000-2,500 ppm, 2,500-3,000 ppm, 3,000-3,500 ppm, 3,500-4,000 ppm,4,000-4,500 ppm, 4,500-5,000 ppm, 5,000-5,500 ppm, 5,500-6,000 ppm,6,000-6,500 ppm, 6,500-7,000 ppm, 7,000-7,500 ppm, 7,500-8,000 ppm,8,000-8,500 ppm, 8,500-9,000 ppm, 9,000-10,000 ppm, 10,000-20,000 ppm,20,000-30,000 ppm, 30,000-40,000 ppm, 40,000-50,000 ppm, 50,000-60,000ppm, 60,000-70,000 ppm, 70,000-80,000 ppm, 80,000-90,000 ppm,90,000-100,000 ppm, 100,000-150,000 ppm, 150,000-200,000 ppm,200,000-250,000 ppm, 250,000-300,000 ppm, 300,000-350,000 ppm,350,000-400,000 ppm, 400,000-450,000 ppm, or 450,000-500,000 ppm. Inother embodiments, the first reagent can comprise from about 50 ppm toabout 40,000 ppm of an ester of a polyhydric alcohol and carboxylicacid, e.g., 50-100, 50-500, 50-1,000, 50-1,500, 50-2,000, 50-2,500,50-3,000, 50-3,500, 50-4,000, 50-4,500, 50-5,000, 50-10,000, 50-20,000,50-30,000, or 50-40,000 ppm of an ester of a polyhydric alcohol andcarboxylic acid.

Hydrogen peroxide (or a source of hydrogen peroxide, such as a substancethat generates hydrogen peroxide upon contact with a liquid) is employedin the second reagent. The peroxycarboxylic acid forming compositionscan comprise any suitable level of hydrogen peroxide or a substance thatgenerates hydrogen peroxide upon contact with a liquid. For example, thesecond reagent of the peroxycarboxylic acid forming composition cancomprise any suitable level of hydrogen peroxide or a source of hydrogenperoxide. In some embodiments, the second reagent can comprise about 1ppm to about 300,000 ppm of hydrogen peroxide or a source of hydrogenperoxide. For example, the second reagent can comprise from about 1-10ppm, 10-20 ppm, 20-30 ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm,70-80 ppm, 80-90 ppm, 90-100 ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm,250-300 ppm, 300-350 ppm, 350-400 ppm, 400-450 ppm, 450-500 ppm, 500-550ppm, 550-600 ppm, 600-650 ppm, 650-700 ppm, 700-750 ppm, 750-800 ppm,800-850 ppm, 850-900 ppm, 900-950 ppm, 950-1,000 ppm, 1,000-1,500 ppm,1,500-2,000 ppm, 2,000-2,500 ppm, 2,500-3,000 ppm, 3,000-3,500 ppm,3,500-4,000 ppm, 4,000-4,500 ppm, 4,500-5,000 ppm, 5,000-5,500 ppm,5,500-6,000 ppm, 6,000-6,500 ppm, 6,500-7,000 ppm, 7,000-7,500 ppm,7,500-8,000 ppm, 8,000-8,500 ppm, 8,500-9,000 ppm, 9,000-10,000 ppm,10,000-20,000 ppm, 20,000-30,000 ppm, 30,000-40,000 ppm, 40,000-50,000ppm, 50,000-60,000 ppm, 60,000-70,000 ppm, 70,000-80,000 ppm,80,000-90,000 ppm, or 90,000-100,000 ppm, 100,000-150,000 ppm,150,000-200,000 ppm, 200,000-250,000 ppm, or 250,000-300,000 ppmhydrogen peroxide or a source of hydrogen peroxide. In otherembodiments, the second reagent comprises from about 150 ppm to about50,000 ppm of hydrogen peroxide or a source of hydrogen peroxide, e.g.,about 150-200, 150-300, 150-400, 150-500, 150-600, 150-700, 150-800,150-900, 150-1,000, 150-1,500, 150-2,000, 150-2,500, 150-3,000,150-3,500, 150-4,000, 150-4,500, 150-5,000, 150-10,000, 50-20,000,50-30,000, 50-40,000 or 50-50,000 ppm of hydrogen peroxide or a sourceof hydrogen peroxide.

The peroxycarboxylic acid forming compositions can include any C1-C18peroxycarboxylic acid, including mixtures of peroxycarboxylic acids,including for example, peroxyformic acid, peroxyacetic acid,peroxyoctanoic acid and/or peroxysulfonated oleic acid. As used herein,the term “peracid” may also be referred to as a “percarboxylic acid,”“peroxycarboxylic acid” or “peroxyacid.” Sulfoperoxycarboxylic acids,sulfonated peracids and sulfonated peroxycarboxylic acids are alsoincluded within the terms “peroxycarboxylic acid” and “peracid” as usedherein. The terms “sulfoperoxycarboxylic acid,” “sulfonated peracid,” or“sulfonated peroxycarboxylic acid” refers to the peroxycarboxylic acidform of a sulfonated carboxylic acid as disclosed in U.S. Pat. No.8,344,026, and U.S. Patent Publication Nos. 2010/0048730 and2012/0052134, each of which are incorporated herein by reference intheir entirety. As one of skill in the art appreciates, a peracid refersto an acid having the hydrogen of the hydroxyl group in carboxylic acidreplaced by a hydroxy group. Oxidizing peracids may also be referred toherein as peroxycarboxylic acids.

A peracid includes any compound of the formula R—(COOOH)_(n) in which Rcan be hydrogen, alkyl, alkenyl, alkyne, acylic, alicyclic group, aryl,heteroaryl, or heterocyclic group, and n is 1, 2, or 3, and named byprefixing the parent acid with peroxy. Preferably R includes hydrogen,alkyl, or alkenyl. The terms “alkyl,” “alkenyl,” “alkyne,” “acylic,”“alicyclic group,” “aryl,” “heteroaryl,” and “heterocyclic group” are asdefined herein. A sulfoperoxycarboxylic acid has the following formula:

wherein R₁ is hydrogen, or a substituted or unsubstituted alkyl group;R₂ is a substituted or unsubstituted alkylene group; X is hydrogen, acationic group, or an ester forming moiety; or salts or esters thereof.In additional embodiments, a sulfoperoxycarboxylic acid is combined witha single or mixed peroxycarboxylic acid composition, such as asulfoperoxycarboxylic acid with peroxyacetic acid and peroxyoctanoicacid (PSOA/POOA/POAA).

In some embodiments, a mixed peracid is employed, such as aperoxycarboxylic acid including at least one peroxycarboxylic acid oflimited water solubility in which R includes alkyl of 5-18 carbon atomsand at least one water-soluble peroxycarboxylic acid in which R includesalkyl of 1-4 carbon atoms. For example, in one embodiment, aperoxycarboxylic acid includes peroxyacetic acid and at least one otherperoxycarboxylic acid such as those named above. Preferably acomposition of the invention includes peroxyformic acid, peroxyaceticacid and/or peroxyoctanoic acid. Other combinations of mixed peracidsare well suited for use in the current invention. Advantageously, acombination of peroxycarboxylic acids provides a composition withdesirable antimicrobial activity in the presence of high organic soilloads. The mixed peroxycarboxylic acid compositions often providesynergistic micro efficacy. Accordingly, compositions of the inventioncan include a peroxycarboxylic acid, or mixtures thereof.

The first or second reagent and the generated liquid peroxycarboxylicacid composition can have any suitable pH range. For example, the firstor second reagent and the generated liquid peroxycarboxylic acidcomposition can have a pH ranging from about 0 to about 11, e.g., about0-1, 0-2, 0-3, 0-4, 0-5, 0-6, 0-7, 0-8, 0-9, 0-10, 0-11, 1-2, 1-3, 1-4,1-5, 1-6, 1-7, 1-8, 1-9, 1-10, 1-11, 2-3, 2-4, 2-5, 2-6, 2-7, 2-8, 2-9,2-10, 2-11, 3-4, 3-5, 3-6, 3-7, 3-8, 3-9, 3-10, 3-11, 4-5, 4-6, 4-7,4-8, 4-9, 4-10, 4-11, 5-6, 5-7, 5-8, 5-9, 5-10, 5-11, 6-7, 6-8, 6-9,6-10, 6-11, 6-7, 7-8, 7-9, 7-10, 7-11, 8-9, 8-10, 8-11, 9-10, 9-11,10-11, or at about 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11. In someembodiments, the first or second reagent and the generated liquidperoxycarboxylic acid composition has a pH ranging from about 5 to about10, e.g., about 5-6, 5-7, 5-8, 5-9, 5-10, 6-7, 6-8, 6-9, 6-10, 7-8, 7-9,7-10, 8-9, 8-10, or 9-10. In other embodiments, the first or secondreagent has a pH at about 9. In other embodiments, the first reagent andthe second reagent are configured to be contacted with each other toform a liquid peroxycarboxylic acid and has a pH at about 9.

The first reagent and the second reagent can be configured to becontacted with each other to form a liquid peroxycarboxylic acid underany suitable conditions or temperature. In some embodiments, the firstreagent and the second reagent are configured to be contacted with eachother under ambient conditions. In other embodiments, the first reagentand the second reagent are configured to be contacted with each at atemperature ranging from about 4° C. to about 60° C., e.g., about 4°C.-5° C., 5° C.-10° C., 10° C.-15° C., 15° C.-20° C., 20° C.-25° C., 25°C.-30° C., 30° C.-35° C., 35° C.-40° C., 40° C.-45° C., 45° C.-50° C.,50° C.-55° C., or 55° C.-60° C. In still other embodiments, the firstreagent and the second reagent are configured to be contacted with eachother to form a liquid peroxycarboxylic acid at a temperature at about4° C. or lower than 4° C., e.g., at about 3° C., 2° C., 1° C., 0° C., orlower than 0° C.

The peroxycarboxylic acid forming compositions can be configured to forma liquid, e.g., a solution, that comprises any suitable level of theperoxycarboxylic acid. For example, the first reagent and the secondreagent in the peroxycarboxylic acid forming compositions can beconfigured to be contacted with each other to form a liquid and/orsolid, e.g., a solution, that comprises any suitable level of theperoxycarboxylic acid. In some embodiments, the first reagent and thesecond reagent can be configured to be contacted with each other to forma liquid, e.g., a solution, that comprises from about 0.1 ppm to about5,000 ppm of peroxycarboxylic acid, e.g., about 0.1-1 ppm, 1-10 ppm,10-20 ppm, 20-30 ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm, 70-80ppm, 80-90 ppm, 90-100 ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm,250-300 ppm, 300-350 ppm, 350-400 ppm, 400-450 ppm, 450-500 ppm, 500-550ppm, 550-600 ppm, 600-650 ppm, 650-700 ppm, 700-750 ppm, 750-800 ppm,800-850 ppm, 850-900 ppm, 900-950 ppm, 950-1,000 ppm, 1,000-1,500 ppm,1,500-2,000 ppm, 2,000-2,500 ppm, 2,500-3,000 ppm, 3,000-3,500 ppm,3,500-4,000 ppm, 4,000-4,500 ppm, or 4,500-5,000 ppm of peroxycarboxylicacid.

In other embodiments, the first reagent and the second reagent can beconfigured to be contacted with each other to form a liquid, e.g., asolution, that comprises from about 1 ppm to about 500 ppm ofperoxycarboxylic acid, e.g., about 0.1-1 ppm, 0.1-10 ppm, 0.1-20 ppm,0.1-30 ppm, 0.1-40 ppm, 0.1-50 ppm, 0.1-60 ppm, 0.1-70 ppm, 0.1-80 ppm,0.1-90 ppm, 0.1-100 ppm, 0.1-150 ppm, 0.1-200 ppm, 0.1-250 ppm, 0.1-300ppm, 0.1-350 ppm, 0.1-400 ppm, 0.1-450 ppm, 0.1-500 ppm ofperoxycarboxylic acid. In still other embodiments, the first reagent andthe second reagent can be configured to be contacted with each other toform a liquid, e.g., a solution, that comprises from about 50 ppm toabout 100 ppm of peroxycarboxylic acid, e.g., about 50-60 ppm, 60-70ppm, 70-80 ppm, 80-90 ppm or 90-100 ppm of peroxycarboxylic acid.

In another example, the solid composition can be configured to becontacted with a liquid to form a solution that comprises from about 0.1ppm to about 5,000 ppm of peroxycarboxylic acid. In some embodiments,the solid composition can be configured to be contacted with a liquid toform a liquid, e.g., a solution, that comprises from about 0.1 ppm toabout 5,000 ppm of peroxycarboxylic acid, e.g., about 0.1-1 ppm, 1-10ppm, 10-20 ppm, 20-30 ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm,70-80 ppm, 80-90 ppm, 90-100 ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm,250-300 ppm, 300-350 ppm, 350-400 ppm, 400-450 ppm, 450-500 ppm, 500-550ppm, 550-600 ppm, 600-650 ppm, 650-700 ppm, 700-750 ppm, 750-800 ppm,800-850 ppm, 850-900 ppm, 900-950 ppm, 950-1,000 ppm, 1,000-1,500 ppm,1,500-2,000 ppm, 2,000-2,500 ppm, 2,500-3,000 ppm, 3,000-3,500 ppm,3,500-4,000 ppm, 4,000-4,500 ppm, or 4,500-5,000 ppm of peroxycarboxylicacid.

The peroxycarboxylic acid forming compositions (liquids or solids) canbe configured to form the resultant compositions comprising any suitablelevel of peroxycarboxylic acid within any suitable time. In someembodiments, the first reagent and the second reagent can be configuredto be contacted with each other to form the peroxycarboxylic acidcomposition that comprises at least about 1 ppm peroxycarboxylic acidwithin 1 minute of the contact time, e.g., at least about 1 ppm, 2 ppm,3 ppm, 4 ppm, 5 ppm, 6 ppm, 7 ppm, 8 ppm, 9 ppm, 10 ppm, 15 ppm, 20 ppm,25 ppm, 30 ppm, 35 ppm, 40 ppm, 45 ppm, 50 ppm, 55 ppm, 60 ppm, 65 ppm,70 ppm, 75 ppm, 80 ppm, 85 ppm, 90 ppm, 95 ppm, 100 ppm, 200 ppm, 300ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm, 1,000 ppm,2,000 ppm, 3,000 ppm, 4,000 ppm, or 5,000 ppm of peroxycarboxylic acidwithin 1 minute, within 5 minutes, within 10 minutes, or greater of thecontact time.

Exemplary Embodiments of Peroxycarboxylic Acid Forming Compositions

In a preferred embodiment for forming a peroxyformic acid composition,the first reagent comprises an ester of a polyhydric alcohol and formicacid, and the second reagent that comprises hydrogen peroxide or thatcomprises a substance that generates hydrogen peroxide when in contactwith a liquid, wherein said first reagent and said second reagent arekept separately prior to use, and when it is time to generateperoxyformic acid, said first reagent and said second reagent areconfigured to be contacted with each other to form a liquid thatcomprises peroxyformic acid and has a pH ranging from about 0 to about11, and pH of the formed liquid becomes about 8 or lower within about 1minute after the contact between said first reagent and said secondreagent. In other embodiments, the present peroxyformic acid formingcomposition comprises a first reagent that comprises an ester of apolyhydric alcohol and formic acid, and a second reagent that comprisesa substance that generates hydrogen peroxide when in contact with aliquid, wherein said first reagent and said second reagent are comprisedin a solid composition, and when it is time to generate peroxyformicacid, said solid composition is configured to be contacted with a liquidto form a liquid that comprises peroxyformic acid and has a pH rangingfrom about 0 to about 11, and pH of the formed liquid becomes about 8 orlower within about 1 minute after the contact between said solidcomposition and said liquid.

In a preferred embodiment for forming a peroxyformic acid compositionthe pH of the formed liquid can become about 8 or lower within about 1minute after the contact between the first reagent and the secondreagent or after the contact between the solid composition and theliquid. In some embodiments, the pH of the formed liquid can becomeabout 8 or lower within about 1 second, 2 seconds, 3 seconds, 4 seconds,5 seconds, 6 seconds, 7 seconds, 8 seconds, 9 seconds, 10 seconds, 20seconds, 30 seconds, 40 seconds, 50 seconds after the contact betweenthe first reagent and the second reagent or after the contact betweenthe solid composition and the liquid. In other embodiments, the pH ofthe formed liquid can become about lower than 1, 2, 3, 4, 5, 6, 7, or 8within about 1 minute after the contact between the first reagent andthe second reagent or after the contact between the solid compositionand the liquid. The liquid that comprises peroxyformic acid can maintainthe pH ranging from about 0 to about 8 for any suitable time after thecontact between the first reagent and the second reagent, or after thecontact between the composition and a liquid. In some embodiments, theliquid that comprises peroxyformic acid maintains the pH ranging fromabout 0 to about 8 from about 1 second to about 10 hours after thecontact between the first reagent and the second reagent or after thecontact between the composition and a liquid. For example, the liquidthat comprises peroxyformic acid can maintain the pH at about 0, 1, 2,3, 4, 5, 6, 7, or 8 from about 1 second to about 10 hours after thecontact between the first reagent and the second reagent or after thecontact between the composition and a liquid. In another example, theliquid that comprises peroxyformic acid can maintain the pH ranging fromabout 0 to about 8 for about 1 second, 2 seconds, 3 seconds, 4 seconds,5 seconds, 6 seconds, 7 seconds, 8 seconds, 9 seconds, 10 seconds, 20seconds, 30 seconds, 40 seconds, 50 seconds, 1 minute, 2 minutes, 3minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9minutes, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 1hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9hours, or 10 hours.

Additional description of preferred embodiments of peroxyformic acidforming compositions, methods of forming the same, and methods of usingthe same are disclosed in U.S. Publication No./Ser. No. 14/973,389titled “Generation of Peroxyformic Acid through Polyhydric AlcoholFormate”, which is herein incorporated by reference in its entirety.

Additional Functional Ingredients

The components of the peroxycarboxylic acid compositions employing theself-indicating chemistry compositions can further include variousfunctional components suitable for use in forming the peroxycarboxylicacid compositions and/or the sanitizing, cleaning and disinfectingapplications of use thereof. In some embodiments, the peroxycarboxylicacid compositions employing the self-indicating chemistry compositionsincluding the self-indicating chemistry compositions and the first andsecond reagents for the peroxycarboxylic acid forming compositions makeup a large amount, or even substantially all of the total weight of theperoxycarboxylic acid compositions. For example, in some embodiments fewor no additional functional ingredients are disposed therein.

In other embodiments, additional functional ingredients may be includedin the compositions. The functional ingredients provide desiredproperties and functionalities to the compositions. For the purpose ofthis application, the term “functional ingredient” includes a materialthat when dispersed or dissolved in a use and/or concentrate solution,such as an aqueous solution, provides a beneficial property in aparticular use. Some particular examples of functional materials arediscussed in more detail below, although the particular materialsdiscussed are given by way of example only, and that a broad variety ofother functional ingredients may be used.

In other embodiments, the compositions may further include a catalyst(e.g. enzyme), stabilizing agents, pH buffering agents, acidulant,defoaming agents, anti-redeposition agents, bleaching agents, solubilitymodifiers, dispersants, wetting agents, metal protecting agents,corrosion inhibitors, additional sequestrants and/or chelating agents,fragrances and/or dyes, rheology modifiers or thickeners, hydrotropes orcouplers, buffers, solvents and the like.

In an aspect, the peroxycarboxylic acid forming compositions can furthercomprise a wetting agent. Wetting agents function to increase thesurface contact or penetration activity of the antimicrobial compositionof the invention. Wetting agents which can be used in the composition ofthe invention include any of those constituents known within the art toraise the surface activity of the composition of the invention. In anexemplary aspect, the wetting agent is a sulfonic acid or salt thereof(e.g., dodecylbenzene sulfonic acid, sodium salt). In certainembodiments, the wetting agent is present in amounts from about 0.001 toabout 10 wt-% wetting agent, about 0.01 to about 1 wt-% wetting agent,about 0.01 to about 0.5 wt-% wetting agent, or about 0.1 to about 0.5wt-% wetting agent.

In an aspect, the peroxycarboxylic acid forming compositions can furthercomprise an acidulant. In an aspect, the acidulant is included in thesecond reagent with hydrogen peroxide. Any suitable acid can be includedin the compositions as an acidulant. In an embodiment the acidulant isan acid or an aqueous acidic solution. In an embodiment, the acidulantincludes an inorganic acid. In some embodiments, the acidulant is astrong mineral acid. Suitable inorganic acids include, but are notlimited to, sulfuric acid, sodium bisulfate, phosphoric acid, nitricacid, hydrochloric acid. In some embodiments, the acidulant includes anorganic acid. Suitable organic acids include, but are not limited to,methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid,butane sulfonic acid, xylene sulfonic acid, cumene sulfonic acid,benzene sulfonic acid, formic acid, acetic acid, mono, di, ortri-halocarboyxlic acids, picolinic acid, dipicolinic acid, and mixturesthereof. In certain embodiments, the acidulant is present in amountsfrom about 0.001 to about 50 wt-% acidulant, about 0.001 to about 10wt-%, about 0.01 to about 1 wt-% acidulant, or about 0.05 to about 0.5wt-%.

In an aspect, the peroxycarboxylic acid forming compositions can furthercomprise a catalyst or an enzyme that catalyzes formation of theperoxycarboxylic acid from the ester of a polyhydric alcohol andcarboxylic acid, and hydrogen peroxide. Any suitable catalyst or enzymecan be included in the peroxycarboxylic acid forming composition, e.g.,a perhydrolytic enzyme, lipase, coronase, termanyl or esperease. Thecatalyst or an enzyme can be comprised in any suitable part of theperoxycarboxylic acid forming compositions. In some embodiments, thefirst reagent comprises the catalyst or enzyme. In other embodiments,the second reagent comprises the catalyst or enzyme. In still otherembodiments, the peroxycarboxylic acid forming compositions can furthercomprise a third reagent that comprises the catalyst or enzyme. In yetother embodiments, the solid composition comprises the catalyst orenzyme.

In an aspect, the peroxycarboxylic acid forming compositions can furthercomprise a stabilizing agent for the peroxycarboxylic acid, astabilizing agent for hydrogen In an aspect, the peroxycarboxylic acidforming compositions can further comprise peroxide, and/or a pHbuffering agent. The present peroxycarboxylic acid forming compositionscan comprise any suitable pH buffering agent stabilizing agent.Exemplary stabilizing agents include a phosphonate salt(s) and/or aheterocyclic dicarboxylic acid, e.g., dipicolinic acid. In someembodiments, the stabilizing agent is pyridine carboxylic acid basedstabilizers, such as picolinic acid and salts, pyridine-2,6-dicarboxylicacid and salts, and phosphonate based stabilizers, such as phosphoricacid and salts, pyrophosphoric acid and salts and most commonly1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) and salts. In otherembodiments, the present peroxycarboxylic acid forming compositionscomprise two or more stabilizing agents, e.g., HEDP and2,6-pyridinedicarboxylic acid (DPA). In an aspect the stabilizingagent(s) can be comprised in any suitable part of the presentperoxycarboxylic acid forming compositions. In some embodiments, thefirst reagent comprises a stabilizing agent for the peroxycarboxylicacid and/or a pH buffering agent. In other embodiments, the secondreagent comprises a stabilizing agent for hydrogen peroxide. In stillother embodiments, the present peroxycarboxylic acid formingcompositions can further comprise a third reagent that comprises astabilizing agent for the peroxycarboxylic acid, a stabilizing agent forhydrogen peroxide, and/or a pH buffering agent. In yet otherembodiments, the solid composition comprises a stabilizing agent forperoxyformic acid, a stabilizing agent for hydrogen peroxide, and/or apH buffering agent.

In an aspect, the peroxycarboxylic acid forming compositions can furthercomprise any suitable pH buffering agent. The pH buffer reagent caninclude any reagent that is compatible with the ester(s) in theperoxycarboxylic acid forming compositions. Exemplary buffer agentssuitable for using with a liquid ester can be an organic amine, such astriethanol amine, imidazole, etc. Exemplary buffer agents suitable forusing with a solid form of ester include a broader range of buffers,such as a carbonate salt, a phosphate salt, etc. The pH buffer reagentcan be comprised in any suitable part of the present peroxyformic acidforming compositions. In some embodiments, the first reagent comprises apH buffering agent. In other embodiments, the peroxycarboxylic acidforming compositions can further comprise a third reagent that comprisesa pH buffering agent. In still other embodiments, the solid compositioncomprises a pH buffering agent.

In an aspect, the peroxycarboxylic acid forming compositions can furthercomprise any suitable stabilizing agent for hydrogen peroxide. Exemplarystabilizing agents for hydrogen peroxide include phosphonates,heterocyclic carboxylic acids and the mixtures thereof. In someembodiments, stabilizing agents for hydrogen peroxide can be Dequest2010, Dequest 2066, Dipicolinic acids, etc. The stabilizing agent forhydrogen peroxide can be comprised in any suitable part of theperoxycarboxylic acid forming compositions. In some embodiments, thesecond reagent comprises a stabilizing agent for hydrogen peroxide. Inother embodiments, the peroxycarboxylic acid forming compositions canfurther comprise a third reagent that comprises a stabilizing agent forhydrogen peroxide. In still other embodiments, the solid compositioncomprises a stabilizing agent for hydrogen peroxide.

In preferred embodiments, the compositions do not include perhydrolysisenzymes, such as members of family 7 of the carbohydrate esterases(CE-7) or a perhydrolysis enzyme, such as those disclosed for example inU.S. Patent Publication 2013/0289113, which is herein incorporated byreference in its entirety.

In preferred embodiments, the compositions do not include iodide, iodineor other components destructive to the peroxycarboxylic acid generatedin situ.

In further embodiments, the latent peracid selective dyes do not includesubstrates for detecting peroxidase in ELISA (Enzyme Linked ImmmunoAssay) applications. Without being limited to a particular mechanism oftheory, the peroxidase does not behave as a perhydrolyase and insteadgenerates OH radicals simulating peracids.

Alkalinity Source

The peroxycarboxylic acid forming compositions may require pH adjustmentwith an alkalinity source. In an exemplary aspect, in the event areagent of the self-indicating peracid chemistry includes an acidiccomponent, such as a wetting agent, an alkalinity source may bedesirable to increase the strongly acidic pH to ensure the perhydrolysisreaction to generate the peroxycarboxylic acid is not slowed.

Suitable sources of alkalinity can include, but is not limited to, analkaline metal hydroxide, an alkaline earth metal hydroxide, an alkalimetal silicate, an alkali metal carbonate, borates, amines, amides orother basic nitrogen sources and mixtures thereof. Suitable alkalinemetal hydroxides include, but are not limited to, sodium hydroxide,potassium hydroxide and mixtures thereof. Suitable alkaline earth metalhydroxides include, but are not limited to, magnesium hydroxide, calciumhydroxide and mixtures and derivatives thereof. Suitable alkali metalsilicates include but are not limited to, sodium silicate andderivatives thereof. Suitable amines include, but are not limited to,primary, secondary or tertiary amines and diamines carrying at least onenitrogen linked hydrocarbon group, which represents a saturated orunsaturated linear or branched alkyl group having at least 1 carbonatom. Amines may further include alkanolamines including, for example,monoethanolamine, monoisopropanolamine, diethanolamine,diisopropanolamine, triethanolamine, triisopropanolamine and the like.

The source of alkalinity can be added to the self-indicating chemistrycompositions to provide the desired pH of the use-solution. In someembodiments, the alkalinity source is added to achieve a pH of fromabout 5 to about 10.

Kits

The self-indicating chemistry composition may be provided in a kit ormulti-part system. In an aspect, a two part spray bottle provides afirst portion of a self-indicating chemistry composition and a secondportion containing a peroxycarboxylic acid or a peroxycarboxylic acidgenerating composition.

In an aspect, a two-part spray bottle is provided for point of useapplication for hard surface disinfection or sanitizing for consumerand/or industrial applications.

In an aspect, a two-part spray bottle is suitable to providecompositions in a variety of delivery forms, including for example,liquids, mist, etc. for consumer and/or industrial applications.

Other Delivery Systems

The self-indicating chemistry composition may be provided in variousforms wherein multi-part systems are provided, preferably two-partsystem.

In an aspect, a two part system may be provided in the form of separatespray bottles, separate storage containers and a device for combiningthe containers, a pre-soaked wipe (or other linen) to be combined with asecond liquid chemistry, or the like.

Kits

In an aspect, the self-indicating chemistry can be provided in a kit fora customer or particular application of use. A kit is particularlyuseful when provided with a color indication system which correlates theobserved color indicator with a range of concentration of theperoxycarboxylic acid composition. A kit can include instructions foruse. In a further aspect, a kit can include information for thecorrelation of a desired wavelength of a visual indicator to aparticular color on a color wheel which is correlated to a ppmconcentration of the peroxycarboxylic acid concentration. The colors ona color wheel can be standardized to a reflective color or to a pantonecolor number (equivalent to a concentration of ppm).

Methods of Indication

Methods of indicating concentrations of a peroxycarboxylic acidcompositions are provided by the self-indicating chemistry compositionsof the invention. In an aspect, the methods including providing aself-indicating chemistry composition to a peroxycarboxylic acidcomposition generated by perhydrolysis in situ, and obtaining variousvisual indicators of the concentration of peroxycarboxylic acidcomposition at points of time. In an aspect, the self-indicatingchemistry compositions provide visual indicators to a user when there isat least an initial efficacious level of the peroxycarboxylic acid (i.e.ready to use), and a subsequent visual indicator when the concentrationof the peroxycarboxylic acid is no longer at an efficacious level (i.e.unsuitable for use). In an aspect, the visual indicators include red,yellow, blue and/or green colors having a correlation to a predeterminedconcentration of a peroxycarboxylic acid. In an aspect, the visualindicators include red, yellow, and green colors having a correlation toa predetermined concentration of a peroxycarboxylic acid. In anotheraspect, the visual indicators include yellow, blue and green colorshaving a correlation to a predetermined concentration of aperoxycarboxylic acid. The methods of the invention can be furtherachieved through the use of a kit for providing the indication ofconcentrations of a peroxycarboxylic acid composition.

The method of indicating concentrations of a peroxycarboxylic acidcompositions includes the combination of self-indicating chemistrycomposition to provide a combination of dyes. The self-indicatingchemistry composition is provided in a two-part system, including afirst part comprising a combination of dyes and an ester precursor forperoxycarboxylic acid generation, and a second part comprising hydrogenperoxide. Additional components of the two-part system are disclosed inthe compositions according to the invention. Without being limited to aparticular mechanism of action, the separation of the two-part systemprevents the hydrogen peroxide from prematurely reacting with the esterprecursor.

In an aspect, the combination of dyes have an initial blue colorindicating the presence of the self-indicating chemistry compositionwith a peroxycarboxylic acid composition or a peroxycarboxylic acidgenerating composition. In an aspect, the visual indicator of the bluedye indicates the presence of the self-indicating chemistry compositionwithin the peroxycarboxylic acid composition or peroxycarboxylic acidgenerating composition. Without being limited to a particular mechanismof action, the blue visual indicator does not directly correlate to anyconcentration of the peroxycarboxylic acid, instead, the blue visualindicator provide by the background dye serves as a background color anda mixing indicator.

In an optional aspect, a red color can be used as an initial indicator.The red color is bleached out of the system promptly upon the initiationof the perhydrolysis reaction and is therefore an optional component ofthe system.

The method of indicating concentrations of a peroxycarboxylic acidcompositions includes at least a second visual indicator. In an aspect,the combination of self-indicating chemistry compositions provides achange from a blue color to a green color to indicate a peroxycarboxylicacid composition is “ready” for use. In an aspect, the change from blueto green indicates a concentration of at least about 1 ppm to 1,000 ppmof the peroxycarboxylic acid.

In an aspect, the peroxycarboxylic acid composition concentrationsmeasured using the self-indicating chemistry compositions provide a userwith a visual indicator to confirm whether a desired peroxycarboxylicacid concentration is retained in a composition. In some embodiments, avisual indicator is provided to confirm a peroxycarboxylic acidcomposition has achieved a suitable concentration, as may be referred toas a minimal inhibitory concentration (MIC) of a particularantimicrobial agent for a surface of contaminated system. In someaspects, a level from about 1 ppm to about 1,000 ppm, e.g., 1-10 ppm,10-20 ppm, 20-30 ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm, 70-80ppm, 80-90 ppm, 90-100 ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm,250-300 ppm, at least about 270 ppm, or at least about 300 ppm, 300-350ppm, 350-400 ppm, 400-450 ppm, 450-500 ppm, 500-550 ppm, 550-600 ppm,600-650 ppm, 650-700 ppm, 700-750 ppm, 750-800 ppm, 800-850 ppm, 850-900ppm, 900-950 ppm, or 950-1,000 ppm.

In an aspect, the peroxycarboxylic acid composition concentrationsmeasured using the self-indicating chemistry compositions provide a userwith a visual indicator to confirm whether a desired peroxycarboxylicacid concentration is obtained in a composition over a pre-determinedamount of time. In some embodiments, a visual indicator is provided toconfirm a peroxycarboxylic acid composition has achieved a suitableconcentration, such as an MIC, within about 30 seconds to about 30minutes, within about 30 seconds to about 10 minutes, from about 30seconds to about 90 seconds, or from about 10 minutes to about 20minutes. In some aspects, a level from about 1 ppm to about 1,000 ppm isdetected with the time frames, e.g., 1-10 ppm, 10-20 ppm, 20-30 ppm,30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm, 70-80 ppm, 80-90 ppm, 90-100ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm, 250-300 ppm, at least about270 ppm, or at least about 300 ppm, 300-350 ppm, 350-400 ppm, 400-450ppm, 450-500 ppm, 500-550 ppm, 550-600 ppm, 600-650 ppm, 650-700 ppm,700-750 ppm, 750-800 ppm, 800-850 ppm, 850-900 ppm, 900-950 ppm, or950-1,000 ppm.

In an exemplary aspect, the peroxycarboxylic acid compositionconcentrations measured using the self-indicating chemistry compositionsprovide a user with a visual indicator to confirm a desiredperoxycarboxylic acid concentration of from about 1 to 100 ppm isobtained in a composition between about 30 seconds to about 90 seconds.In a further exemplary aspect, the peroxycarboxylic acid compositionconcentrations measured using the self-indicating chemistry compositionsprovide a user with a visual indicator to confirm a desiredperoxycarboxylic acid concentration of from about 1 to 10 ppm isobtained in a composition between about 10 minutes to about 20 minutes.

The method of indicating concentrations of a peroxycarboxylic acidcomposition includes at least a third visual indicator. In an aspect,the combination of self-indicating chemistry compositions provides achange from a green color to a yellow color to indicate aperoxycarboxylic acid composition or concentration is no longer suitablefor use or an “exhausted” composition.

In an aspect, the peroxycarboxylic acid composition concentrationsmeasured using the self-indicating chemistry compositions provide a userwith a visual indicator to confirm when a desired peroxycarboxylic acidconcentration is no longer retained. In some embodiments, a visualindicator is provided to confirm when a peroxycarboxylic acidcomposition has reduced by a percentage over a period of time. In someaspects, a visual indicator is provided to indicate a desiredperoxycarboxylic acid concentration has reduced by 10%, 15%, 20%, 25%,30%, 35%, 40%, 45%, 50%, or greater from the initial peroxycarboxylicacid activity or concentration on a predetermined amount of time, whichcorrelates with a visual indicator based on the fading or changing incolor of a selected dye of the self-indicating peroxycarboxylic acidchemistry.

In an aspect, the visual indicators provided according to the inventionmay be further combined with a system to monitor the peroxycarboxylicacid compositions. The compositions can be further monitored in anysuitable manner. For example, sensor technologies may be used incombination with an optical sensor technology. In an aspect, and withoutlimiting the scope of the monitoring which one skilled in the art willascertain based upon the disclosure herein, the monitor, such as asensor, may also be used to determine the concentrations ofperoxycarboxylic acid or other components of the composition (e.g.hydrogen peroxide, or other additional ingredients, such as acidulants,one or more stabilizing agents, surfactants, adjuvants, solvents,additional antimicrobial agents or other ingredients which may bepresent in the composition).

In an alternative aspect, the methods of indicating concentrations of aperoxycarboxylic acid composition could be employed for detectedmaintained peroxycarboxylic acid concentration in a ready-to-use orpre-formed composition. In such an embodiment, the visual indicators mayinclude for example, a two or more color system to indicate aready-to-use, or first, desired concentration of the peroxycarboxylicacid, and thereafter a second visual indicator once the peroxycarboxylicacid concentration drops below a threshold concentration suitable for aparticular use.

Methods of Use

In an aspect, the self-indicating chemistry compositions andperoxycarboxylic acid compositions employing the self-indicatingchemistry compositions are suitable for use in industries andapplications where sanitizing, cleaning or disinfecting compositions areemployed. Beneficially, the self-indicating chemistry compositions arenon-destructive assays for peroxycarboxylic acid compositions. As aresult, the self-indicating chemistry compositions unexpectedly providea non-destructive mechanism to monitor biocide concentrations withoutdestruction of the biocide itself, serving as a benign probe or assay ofthe chemistries. As referred to herein, non-destructive means that thedyes do not result in any more than stoichiometric damage or loss of theperoxycarboxylic acid concentration. In an aspect, non-destructivefurther means that the dyes do not result in loss of theperoxycarboxylic acid concentration at a rate that exceeds the ongoinggeneration of peroxycarboxylic acid in an in situ reaction for theongoing generation of the biocide.

In further aspects, the self-indicating chemistry compositionsunexpectedly provide a stabilizing effect on the in situ generatedperoxycarboxylic acid compositions. In an aspect the peroxycarboxylicacid compositions employing the self-indicating chemistry compositionsaccording to the invention result in at least about 1%, 2%, 3%, 4%, 5%,6%, 7%, 8%, 9%, or at least a 10% improvement in peroxycarboxylic acidstabilization in comparison to an in situ generated peroxycarboxylicacid composition not employing the self-indicating chemistry. In otheraspects, the peroxycarboxylic acid compositions employing theself-indicating chemistry compositions according to the invention resultin at least about 10%, or at least about 15%, or at least about 20%, orat least about 25% improvement in peroxycarboxylic acid stabilization incomparison to an in situ generated peroxycarboxylic acid composition notemploying the self-indicating chemistry. As referred to herein, theimprovement in peroxycarboxylic acid stabilization refers to theconcentration of peroxycarboxylic acid (ppm) retained in the compositionover time, such as over 5 minutes, 10 minutes, 15 minutes, 20 minutes orlonger from the in situ reaction to generate the peroxycarboxylic acidcomposition.

In an aspect, use of a peroxycarboxylic acid for sanitizing, cleaning ordisinfecting, including use on a target surface, such as hard surfacesis particularly suitable for employing the methods of indicationdisclosed herein. Applications to a target, including a hard surface,include contacting a target with an effective amount of peroxycarboxylicacid, wherein the effective amount is indicated to a user by theself-indicating chemistry composition, and said contacting step lastsfor sufficient time to stabilize or reduce microbial population inand/or on said target or said treated target composition. Examplesinclude at least a portion of a medium, a container, a surface, anequipment, including those in a facility for producing, growing,holding, processing, packaging, storing, or transporting a food orbeverage item or pulp, transporting, preparing, cooking or serving afood or beverage item or the plant item. Further examples, include anymedium, a surface, a container, an equipment, or a system in a healthcare facility, e.g., a physical office or a hospital. A still furtherexample includes a biofilm on a surface.

In further aspects, the target or surface may include any suitable fooditem. For example, the food item can be an animal product, e.g., ananimal carcass or an egg, a fruit item, a vegetable item, or a grainitem. In still further aspects, the target or surface may include anysuitable plant item. In some embodiments, the plant item is a grain,fruit, vegetable or flower plant item. In other embodiments, the plantitem is a living plant item or a harvested plant item. In still otherembodiments, the plant item comprises a seed, a tuber, a growing plant,a cutting, or a root stock. In yet other embodiments, the presentmethods are used for treating a living plant tissue comprising treatingthe plant tissue with the above composition in a diluted level tostabilize or reduce microbial population in and/or on the plant tissue.

In some aspects, the present methods are particularly suitable fortreating a target that is at least a portion of a container, anequipment, a system or a facility for holding, processing, packaging,storing, transporting, preparing, cooking or serving the food item orthe plant item. In some embodiments, the target is at least a portion ofa container, an equipment, a system or a facility for holding,processing, packaging, storing, transporting, preparing, cooking orserving a meat item, a fruit item, a vegetable item, or a grain item. Inother embodiments, the target is at least a portion of a container, anequipment, a system or a facility for holding, processing, packaging,storing, or transporting an animal carcass. In still other embodiments,the target is at least a portion of a container, an equipment, a systemor a facility used in food processing, food service or health careindustry. In yet other embodiments, the target is at least a portion ofa fixed in-place process facility. An exemplary fixed in-place processfacility can comprise a milk line dairy, a continuous brewing system, apumpable food system or a beverage processing line. In yet otherembodiments, the solid surface is an inanimate solid surface which maybe contaminated by a biological fluid, e.g., a biological fluidcomprising blood, other hazardous body fluid, or a mixture thereof. Inother embodiments, the solid surface can be a contaminated surface. Anexemplary contaminated surface can comprise the surface of food servicewares or equipment, or the surface of a fabric.

The present methods may be useful in the cleaning or sanitizing ofcontainers, processing facilities, or equipment in the food service orfood processing industries. The present methods may be used on foodpackaging materials and equipment, including for cold or hot asepticpackaging. Examples of process facilities in which the present methodsmay be employed include a milk line dairy, a continuous brewing system,food processing lines such as pumpable food systems and beverage lines,etc. Food service wares may be disinfected with the present methods. Forexample, the present methods may also be used on or in ware washmachines, dishware, bottle washers, bottle chillers, warmers, third sinkwashers, cutting areas (e.g., water knives, slicers, cutters and saws)and egg washers. Particular treatable surfaces include packaging such ascartons, bottles, films and resins; dish ware such as glasses, plates,utensils, pots and pans; ware wash machines; exposed food preparationarea surfaces such as sinks, counters, tables, floors and walls;processing equipment such as tanks, vats, lines, pumps and hoses (e.g.,dairy processing equipment for processing milk, cheese, ice cream andother dairy products); and transportation vehicles. Containers includeglass bottles, PVC or polyolefin film sacks, cans, polyester, PEN or PETbottles of various volumes (100 ml to 2 liter, etc.), one gallon milkcontainers, paper board juice or milk containers, etc.

In an aspect, the peroxycarboxylic acid contacts a target forsanitizing, cleaning or disinfecting at any suitable level of saidperoxycarboxylic acid, e.g., about 0.1-1 ppm, 1-10 ppm, 10-20 ppm, 20-30ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm, 70-80 ppm, 80-90 ppm,90-100 ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm, 250-300 ppm, 300-350ppm, 350-400 ppm, 400-450 ppm, 450-500 ppm, 500-550 ppm, 550-600 ppm,600-650 ppm, 650-700 ppm, 700-750 ppm, 750-800 ppm, 800-850 ppm, 850-900ppm, 900-950 ppm, 950-1,000 ppm, 1,000-1,500 ppm, 1,500-2,000 ppm,2,000-2,500 ppm, 2,500-3,000 ppm, 3,000-3,500 ppm, 3,500-4,000 ppm,4,000-4,500 ppm, or 4,500-5,000 ppm, 5,000-5,500 ppm, 5,500-6,000 ppm,6,000-6,500 ppm, 6,500-7,000 ppm, 7,000-7,500 ppm, 7,500-8,000,8,000-8,500 ppm, 8,500-9,000 ppm, 9,000-9,500 ppm, or 9,500-10,000 ppmof peroxycarboxylic acid.

In an aspect, the peroxycarboxylic acid composition is used for suchtarget or hard surface treatment until the self-indicating chemistrycompositions provides a user with a visual indicator that the suitablelevel (concentration) or percentage of the peroxycarboxylic acid isretained in the composition. In some embodiments, the peroxycarboxylicacid composition retains at least about 50%, 55%, 60%, 65%, 70%, 75%,80%, 85% or 90% of the initial peroxycarboxylic acid activity before auser receives the visual indication that the peroxycarboxylic acidcomposition is no longer suitable for use.

The present methods may be useful in treating a water source as atarget. The present methods can be used to treat water, and the presentmethods can comprise providing an effective amount of peroxycarboxylicacid formed using the above methods to a water source in need oftreatment to form a treated water source, wherein said treated watersource comprises from about 0.1-1 ppm, 1-10 ppm, 10-20 ppm, 20-30 ppm,30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm, 70-80 ppm, 80-90 ppm, 90-100ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm, 250-300 ppm, 300-350 ppm,350-400 ppm, 400-450 ppm, 450-500 ppm, 500-550 ppm, 550-600 ppm, 600-650ppm, 650-700 ppm, 700-750 ppm, 750-800 ppm, 800-850 ppm, 850-900 ppm,900-950 ppm, or 950-1,000 ppm. The present methods can be used to treatany suitable water source. For example, a water source in need oftreatment can be fresh water, pond water, sea water, produced water,paper manufacturing water, tower water or a combination thereof. In someembodiments, the tower water is cooling water and the treated watersource comprises from about 1 ppm to about 10 ppm of the peroxyformicacid, e.g., about 1-2 ppm, 2-3 ppm, 3-4 ppm, 4-5 ppm, 5-6 ppm, 6-7 ppm,7-8 ppm, 8-9 ppm, or 9-10 ppm peroxyformic acid. The contacting step canlast any suitable amount of time, e.g., about 1-2 minutes, 2-3 minutes,3-4 minutes, 4-5 minutes, 5-6 minutes, 6-7 minutes, 7-8 minutes, 8-9minutes, or 9-10 minutes. The contacting step can be conducted atsuitable temperature range. For example, the contacting step can beconducted at a temperature ranging from about 0° C. to about 60° C.,e.g., about 0° C.-1° C., 1° C.-2° C., 2° C.-3° C., 3° C.-4° C., 4° C.-5°C., 5° C.- 10° C., 10° C.-15° C., 15° C.-20° C., 20° C.-25° C., 25°C.-30° C., 30° C.-35° C., 35° C.-40° C., 40° C.-45° C., 45° C.-50° C.,50° C.-55° C., or 55° C.-60° C.

In some embodiments, the present methods can be used to treat a watersource used in oil or gas drilling operation. For example, the presentmethods can be used to treat a water source used in an operation ofinduced hydraulic fracturing (hydrofracturing or fracking). The watersource can comprise a friction reducer or a viscosity enhancer. Thepresent methods can be used to treat a water source to form a treatedwater source that comprises from about 1 ppm to about 10 ppm of theperoxyformic acid, e.g., about 1-2 ppm, 2-3 ppm, 3-4 ppm, 4-5 ppm, 5-6ppm, 6-7 ppm, 7-8 ppm, 8-9 ppm, or 9-10 ppm or greater peroxycarboxylic.The present methods can further comprise disposing of the treated watersource. The present methods can further comprise directing the treatedwater source into a subterranean environment, e.g., a subterraneanenvironment that comprises a well in a gas and/or oil.

The methods include any suitable manner of applying the peroxycarboxylicacid compositions. In some embodiments, the peroxycarboxylic acid can beapplied to a target by means of a spray, a fog, or a foam, or by dippingall or part of the target in a composition comprising theperoxycarboxylic acid. In some embodiments, the peroxycarboxylic acidcomposition is applied to the target by means of a spray, a fog, or afoam. In other embodiments, the diluted peroxycarboxylic acid is appliedto the target by applying in the form of a thickened or gelled solution.In still other embodiments, all or part of the target is dipped in theperoxycarboxylic acid composition. The target and/or theperoxycarboxylic acid composition can be subject to any suitablemovement to help or facilitate the contact between the target and theperoxycarboxylic acid composition. In some embodiments, theperoxycarboxylic acid composition can be agitated. In other embodiments,the peroxycarboxylic acid composition can be sprayed onto a target.

The contacting step of the present methods can last for any suitableamount of time. In some embodiments, the contacting step can last for atleast about 10 seconds. For example, the contacting step can last for atleast about 10, 20, 30, 40, 50 seconds, 1 minute, 1-2 minutes, 2-3minutes, 3-4 minutes, 4-5 minutes, 5-6 minutes, 6-7 minutes, 7-8minutes, 8-9 minutes, or 9-10 minutes, 10-15 minutes, 15-20 minutes,20-25 minutes, 25-30 minutes, 30-40 minutes, 40-50 minutes, 50-65minutes, 1-2 hours, 2-3 hours, 3-4 hours, 4-5 hours, 5-6 hours, 6-7hours, 7-8 hours, 8-9 hours, or 9-10 hours, 16 hours, 1 day, 3 days, 1week, or longer.

The present methods can be used to reduce microbial population in and/oron the target or the treated target composition by any suitablemagnitude. In some embodiments, the present methods can be used toreduce microbial population in and/or on the target or surface by atleast one log 10, two log 10, three log 10, four log 10, five log 10, ormore. In other embodiments, the level of a microorganism, if present inand/or on the target or surface, can be stabilized or reduced by thepresent methods. For example, at least 10%, 20%, 30%, 40%, 50%, 60%,70%, 80%, or 90% or more of the microorganism can be killed, destroyed,removed and/or inactivated by the present methods. The present methodscan be used to reduce population of any suitable microbe(s) by anysuitable magnitude. The peroxycarboxylic acid compositions provide broadspectrum bactericidal and fungistatic activity. For example, theperoxycarboxylic acid compositions provide broad spectrum activityagainst wide range of different types of microorganisms (including bothaerobic and anaerobic microorganisms), including bacteria, yeasts,molds, fungi, algae, and other problematic microorganisms. Exemplarymicroorganisms susceptible to the peroxycarboxylic acid compositionsinclude, gram positive bacteria (e.g., Staphylococcus aureus, Bacillusspecies (sp.) like Bacillus subtilis, Clostridia sp.), gram negativebacteria (e.g., Escherichia coli, Pseudomonas sp., Klebsiellapneumoniae, Legionella pneumophila, Enterobacter sp., Serratia sp.,Desulfovibrio sp., and Desulfotomaculum sp.), yeasts (e.g.,Saccharomyces cerevisiae and Candida albicans), molds (e.g., Aspergillusniger, Cephalosporium acremonium, Penicillium notatum, and Aureobasidiumpullulans), filamentous fungi (e.g., Aspergillus niger and Cladosporiumresinae), algae (e.g., Chlorella vulgaris, Euglena gracilis, andSelenastrum capricornutum), and other analogous microorganisms andunicellular organisms (e.g., phytoplankton and protozoa).

In an aspect, the present methods provide an indication ofperoxycarboxylic acid concentration suitable for the biocidal efficacyagainst C. difficiles spores, namely at least about 270 ppm, orpreferably at least about 300 ppm peroxycarboxylic acid.

The present methods can be conducted at any suitable temperature range.In some embodiments, the present methods can be conducted at atemperature ranging from about 0° C. to about 70° C., e.g., from about0° C. to about 4° C. or 5° C., from about 5° C. to about 10° C., fromabout 11° C. to about 20° C., from about 21° C. to about 30° C., fromabout 31° C. to about 40° C., including at about 37° C., from about 41°C. to about 50° C., from about 51° C. to about 60° C., or from about 61°C. to about 70° C. In other embodiments, the present methods can beconducted at a temperature at or lower than 0° C.

In an exemplary method of use, the compositions are useful in thecleaning or sanitizing of processing facilities or equipment in the foodservice, food processing or health care industries. Examples of processfacilities in which the present methods can be employed include a milkline dairy, a continuous brewing system, food processing lines such aspumpable food systems and beverage lines, etc. Food service wares canalso be disinfected with the present methods. The present methods arealso useful in sanitizing or disinfecting solid surfaces such as floors,counters, furniture, medical tools and equipment, etc., found in thehealth care industry. Such surfaces often become contaminated withliquid body spills such as blood, other hazardous body fluids ormixtures thereof. Generally, the actual cleaning of the in-place systemor other surface (i.e., removal of unwanted offal therein) can beaccomplished with a different material such as a formulated detergentwhich is introduced with heated water. After this cleaning step, theperoxycarboxylic acid composition can be applied or introduced into thesystem at a use solution concentration in unheated, ambient temperaturewater. In some embodiments, the peroxycarboxylic acid composition isfound to remain in solution in cold (e.g., 40° F./4° C.) water andheated (e.g., 140° F./60° C.) water. Although it is not normallynecessary to heat the aqueous use solution of the peroxycarboxylic acidcomposition, under some circumstances heating may be desirable tofurther enhance its antimicrobial activity.

In another exemplary method of use, a method of sanitizing substantiallyfixed in-place process facilities comprises the following steps. Theperoxycarboxylic acid composition of the present invention is introducedinto the process facilities at a temperature in the range of about 4° C.to about 60° C. After introduction of the use solution, the solution iscirculated throughout the system for a time sufficient to sanitize theprocess facilities (i.e., to kill undesirable microorganisms). After thesystem has been sanitized by means of the present composition, the usecomposition or solution is drained from the system. Upon completion ofthe sanitizing step, the system optionally may be rinsed with othermaterials such as potable water. The present composition is preferablycirculated through the process facilities for 10 minutes or less.

In yet another exemplary method of use, the peroxycarboxylic acidcompositions may also be employed by dipping food processing equipmentinto the diluted (or use) composition or solution of the presentinvention, soaking the equipment for a time sufficient to sanitize theequipment, and wiping or draining excess solution off the equipment. Thecomposition may be further employed by spraying or wiping foodprocessing surfaces with the use solution, keeping the surfaces wet fora time sufficient to sanitize the surfaces, and removing the excesscomposition or solution by wiping, draining vertically, vacuuming, etc.

In still other exemplary methods of use, the present peroxycarboxylicacid composition may also be used in a method of sanitizing hardsurfaces such as institutional type equipment, utensils, dishes, healthcare equipment or tools, and other hard surfaces. The presentperoxyformic acid composition may also be employed in sanitizingclothing items or fabric which has become contaminated. Theperoxycarboxylic acid composition is contacted with any of the abovecontaminated surfaces or items at use temperatures in the range of about4° C. to about 60° C. for a period of time effective to sanitize,disinfect, or sterilize the surface or item.

All publications and patent applications in this specification areindicative of the level of ordinary skill in the art to which thisinvention pertains. All publications and patent applications are hereinincorporated by reference to the same extent as if each individualpublication or patent application was specifically and individuallyindicated as incorporated by reference.

EXAMPLES

Embodiments of the present invention are further defined in thefollowing non-limiting Examples. It should be understood that theseExamples, while indicating certain embodiments of the invention, aregiven by way of illustration only. From the above discussion and theseExamples, one skilled in the art can ascertain the essentialcharacteristics of this invention, and without departing from the spiritand scope thereof, can make various changes and modifications of theembodiments of the invention to adapt it to various usages andconditions. Thus, various modifications of the embodiments of theinvention, in addition to those shown and described herein, will beapparent to those skilled in the art from the foregoing description.Such modifications are also intended to fall within the scope of theappended claims.

Example 1

The two-part chemistry system of was evaluated for its ability toprovide self-indicating detection of changes in concentration ofperoxycarboxylic acid concentrations in a solution produced in situ. Inthis example performic acid was generated in situ as theperoxycarboxylic acid composition.

Part (I):

Glyceryl formate 97.0996% Imidazole 2.7673%3,3′,5,5′-Tetramethylbenzidine (TMB) 0.0466%2,2′-azino-bis(3-ethylbenzothiazoline- 0.0748% 6-sulphonic acid) (ABTS)FD&C Blue #1 0.0117%Part (II):

hydrogen peroxide, 50% aq. 6.0000% dodecylbenzene sulfonic acid, sodiumsalt 0.2000% dipicolinic acid 0.0500% (pH adjusted to 2.65 with NaOH)The in situ peracid generator combined: Part (I) 3.5% of a 50% H₂O₂ andPart (II) 96.5%. The two parts were blended together at about 20° C. Theinitial combination resulted in the FD&C blue dye mixing into the othersolution, providing a visualization of mixing, followed by a rapid(30-60 seconds) transition from blue to green. The green color indicatesthe performic acid has reached a concentration of about 300 ppm (alsoindicative of the use solution reaching a lethal for C-diff spores).Following from about 48 to 72 hours from combination of the two-partsystem, both of the yellow dyes and the FD&C blue dye fade, indicatingthe useful life of product has expired.

Example 2

The self-indicating peroxycarboxylic acid chemistry formula of Example 1was produced as described as a two part mixture followed by severalseconds of mixing and immediate placement in the 1 cm cell. Scans wererun at 30 second intervals beginning immediately.

FIG. 1 shows a graph of a UV-VIS scans at 30 second intervals showingrespective absorptions of the dyes employed for the self-indicatingchemistry for use with the peroxycarboxylic acid compositions. As shown,the 410 nm peak grows with time (yellow indicator in the peracidcomposition) while the 620 nm peak (blue color indicator in the peracidcomposition) fades very slowly.

Example 3

The two-part chemistry system of was evaluated for its ability toprovide self-indicating detection of changes in concentration ofperoxycarboxylic acid concentrations in a solution produced in situ. Inthis example performic acid was generated in situ as theperoxycarboxylic acid composition.

Ester Pre-Mix:

Ethyl formate 57.0000% Glyceryl triformate 41.6559% Imidazole 1.2900%TMB 0.0200% ABTS 0.0317% FD&C Blue #1 0.0024%

The pre-mix was added in the quantity of 3.5 g to 97.0 g of a 3%hydrogen peroxide solution. The final latent peracid selective dyes andbackground dye were present at the following use levels:

Use Levels

Description wt % ppm (w/w) TMB 0.00060 6.0 ABTS 0.00095 9.5 FD&C Blue #10.00007 0.7

Beneficially, the in situ peracid generator resulted in the FD&C bluedye mixing into the other solution, providing a visualization of mixing,followed by a rapid transition from blue to green. The green colorindicates the performic acid has reached a concentration of about 300ppm (also indicative of the use solution reaching a lethal for C-diffspores). Following from about 48 to 72 hours from combination of thetwo-part system, both of the yellow dyes and the FD&C blue dye fade,indicating the useful life of product has expired.

Example 4

The self-indicating chemistry system was further evaluated to confirmthe non-destructive nature of the self-indicating systems on the peracidcompositions employed for antimicrobial and other applications of use.In this example the extent of destruction of the peracid concentrationwas evaluated as a result of the interaction with the dyes of theindicating systems. The concentration of peroxyformic acid was evaluatedover time (up to 20 minutes) after addition of the color dyes, as shownin FIG. 2 . Surprisingly, as shown in the graph of FIG. 2 the dyes havea stabilizing effect on the peracid.

The evaluated formulations are shown below:

PFA Part (I): Dye

Glyceryl formate 97.0643% Imidazole 2.7964%3,3′,5,5′-Tetramethylbenzidine (TMB) 0.0513%2,2′-azino-bis(3-ethylbenzothiazoline- 0.0766% 6-sulphonic acid) (ABTS)FD&C Blue #1 0.0115%PFA Part (II): Peroxide Activator

hydrogen peroxide, 50% aq. 96.0025% dodecylbenzene sulfonic acid, sodiumsalt 3.2001% dipicolinic acid 0.7975% (pH adjusted to 2.65 with NaOH)

The on-site peracid generation was tested combining 3.5 wt-% Part I(dye) and 96.5 wt-% Part II (peroxide activator).

Control Part (I): Dye

Glyceryl formate 94.5267% Imidazole 5.4733% No dyes presentControl Part (II): Peroxide Activator

hydrogen peroxide, 50% aq. 96.0025% dodecylbenzene sulfonic acid, sodiumsalt 3.2001% dipicolinic acid 0.7975% (pH adjusted to 2.65 with NaOH)

The on-site peracid generation for the control was tested combining 3.5wt-% Part I (control-no dye) and 96.5 wt-% Part II (peroxide activator).

The data depicted in FIG. 2 is shown in Table 2.

TABLE 2 PFA- PFA- PFA-A1 PFA-A2 Control 1 Control 2 Time(min) (ppm)(ppm) (ppm) (ppm) 1 2273 2268 2589 2577 3 2642 2618 2473 2382 5 24592558 2325 2325 20 2164 2264 1566 1535 47 1691 1683

Example 5

The self-indicating chemistry system was further evaluated to assess thehalf-lives of exemplary latent and pre-existing dyes suitable for useaccording to embodiments of the invention, as shown in Table 3.

TABLE 3 Half-Life of Dyes pre-existing Dye Cone. λ max Max (minutes orlatent dyes (ppm) (nm) Absorbance at 20° C.) TMB 233 410-420 0.40 3 ABTS374 410-421 0.34 420 FD&C Blue #1 55 630 0.25 60 Performic GeneratingPortion: wt. % Formyl glyceride(s) 1.5 Hydrogen peroxide 3 Adjuvants:Conc., ppm Imidazole 236 DDBSA 2000 Dipicolinic acid 500

Further experimentation of the combination of components shown in Table3 was evaluated. When the yellow TMB signal is generated and mixed withthe first yellow dye formed, “oxidized” TMB, and later “oxidized”: ABTSthe result is a bright green (as can be readily interpreted as a visual“ready” signal) due to mixing of yellow with the pre-existing blue. Forthe dyes in Table 3 after approximately 60 minutes the pre-existing bluefades while the devoped yellow from the more rugged latent dye of ABTSbecomes dominant in the mixture. The resulting dominant color of yellowmay be interpreted as a readily interpreted visual “warning” of peracidexhaustion, providing desirable visual indicators of the concentrationof the peracid composition concentration. A visual depiction of thiscolor development and bleackign or oxidizing is shown in FIG. 3 .

The inventions being thus described, it will be obvious that the samemay be varied in many ways. Such variations are not to be regarded as adeparture from the spirit and scope of the inventions and all suchmodifications are intended to be included within the scope of thefollowing claims. The above specification provides a description of themanufacture and use of the disclosed compositions and methods. Sincemany embodiments can be made without departing from the spirit and scopeof the invention, the invention resides in the claims.

What is claimed is:
 1. A self indicating peroxycarboxylic acid chemistrycomposition comprising: a peroxycarboxylic acid; a background dye; andat least two latent peracid selective dyes which upon oxidation by theperoxycarboxylic acid provides a tri-color visual indication of thepresence of a minimum concentration of peroxycarboxylic acid forefficacy as an antimicrobial, wherein the composition is free of iodide,and wherein the combination of dyes have different half-lives to providesustained visual indication of peroxycarboxylic acid concentration forat least 12 hours.
 2. The composition of claim 1, wherein at least onedye is a horse radish peroxidase enzyme (HRP) substrate.
 3. Thecomposition of claim 2, wherein the HRP substrate is p-NitrophenylPhosphate, Disodium Salt, 2,2′-Azinobis[3-ethylbenzothiazoline-6-sulfonic acid]-diammonium salt,o-phenylenediamine dihydrochloride, 3,3′,5,5′-tetramethylbenzidine, orcombinations thereof.
 4. The composition of claim 1, wherein thebackground dye is produced using aromatic hydrocarbons from petroleum.5. The composition of claim 1, wherein the latent peracid selectivedye(s) is non-destructive to the peroxycarboxylic acid and/or providesat least about 10% improvement in peroxycarboxylic acid stabilization incomparison to a peroxycarboxylic acid composition not employing the dyeas measured by concentration (ppm) of the peroxycarboxylic acid retainedin the composition over at least 10 minutes.
 6. The composition of claim1, wherein the peroxycarboxylic acid is a C1-C18 peroxycarboxylic acid.7. The composition of claim 1, further comprising at least oneadditional functional ingredient selected from the group consisting of acatalyst, stabilizing agent, pH buffering agent, acidulant, defoamingagent, anti-redeposition agent, bleaching agent, solubility modifier,dispersant, wetting agent, metal protecting agent, corrosion inhibitor,additional sequestrant and/or chelating agent, fragrance, dye, rheologymodifier or thickener, hydrotrope or coupler, solvent and combinationsthereof.
 8. A kit comprising: a first reagent comprising at least oneester of a polyhydric alcohol and a C1-C18 carboxylic acid; a secondreagent comprising hydrogen peroxide or a substance that generateshydrogen peroxide; and a non-fluorescent visual indicator comprising atleast three dyes for providing a tri-color visual color indicationcorrelated to a concentration of peroxycarboxylic acid, wherein thevisual indicator can be a third reagent or combined with the firstreagent, wherein the combination of dyes have different half-lives toprovide sustained visual indication of peroxycarboxylic acidconcentration for at least 12 hours; wherein combining the first reagentand the second reagent generates a peroxycarboxylic acid in situ byperhydrolysis reaction and the presence of the non-fluorescent visualindicator provides a color indication of the presence of a minimumconcentration of the peroxycarboxylic acid for surface disinfection,wherein the kit is free of iodide.
 9. The kit of claim 8, wherein atleast one of the dyes is a horse radish peroxidase enzyme (HRP)substrate comprising p-Nitrophenyl Phosphate, Disodium Salt,2,2′-Azinobis [3-ethylbenzothiazoline-6-sulfonic acid]-diammonium salt,o-phenylenediamine dihydrochloride, 3,3′,5,5′-tetramethylbenzidine, orcombinations thereof, and wherein at least one of the dyes is abackground dye produced using aromatic hydrocarbons from petroleum. 10.The kit of claim 9, further comprising instructions for use including acolor indicator for comparing the color of the visual indicator to apredefined concentration of peroxycarboxylic acid generated from theperhydrolysis reaction.
 11. The kit of claim 9, wherein the combinedweight percentages of the first and second reagents comprise from about0.1-50 wt-% of the ester of the polyhydric alcohol and C1-C18 carboxylicacid, from about 0.1-50 wt-% of the hydrogen peroxide or substance thatgenerates hydrogen peroxide and from about 0.0001-5 wt-% of the dyes.